Microcapsule comprising a polyester-urethane shell and a hydrophobic core material

ABSTRACT

Disclosed herein are microcapsules as core-shell-particles, including a polymeric shell, a method of making them, a dispersion of those microcapsules in a liquid medium and use thereof. The microcapsules include a core that contains a hydrophobic component.

The present invention relates to microcapsules as acore-shell-particles, comprising a polymeric shell, a method of makingthem, a dispersion of those microcapsules in a liquid medium and the usethereof. The microcapsules comprise a core that contains a hydrophobiccomponent.

Microcapsules are spherical objects which consist of a core and a wallmaterial surrounding the core, wherein the core in principal can be asolid, liquid or gaseous component which is surrounded by the solid wallmaterial. For many applications the wall is formed by a polymermaterial. Microcapsules usually have a volume average diameter from 1 to1000 μm.

A multitude of shell materials is known for producing the wall ofmicrocapsules. The shell can consist either of natural, semisynthetic orsynthetic materials. Natural shell materials are, for example, gumarabic, agar agar, agarose, maltodextrins, alginic acid or its salts,e.g. sodium alginate or calcium alginate, fats and fatty acids, cetylalcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac,polysaccharides, such as starch or dextran, polypeptides, proteinhydrolyzates, sucrose and waxes. Semisynthetic shell materials are interalia chemically modified celluloses, in particular cellulose esters andcellulose ethers, e.g. cellulose acetate, ethyl cellulose,hydroxypropylcellulose, hydroxypropylmethylcellulose andcarboxymethyl-cellulose, and also starch derivatives, in particularstarch ethers and starch esters. Synthetic shell materials are, forexample, polymers, such as polyacrylates, polyamides, polyvinylalcohols, polyvinylpyrrolidones or polyureas.

Depending on the type of shell material and the production process,microcapsules are formed in each case with different properties, such asdiameter, size distribution and physical and/or chemical properties.

Polyurea core-shell microcapsules obtained by reaction of at least onediisocyanate and at least one polyamine are well known in the art, forexample from WO 2011/161229 or WO 2011/160733. According to WO2011/161229 or WO 2011/160733 the polyurea microcapsules are prepared inpresence of polyvinylpyrrolidone (PVP) as a protective colloid.

The development of biodegradable microcapsules was carried out mainlyfor drug transport and in-vivo release applications. Attention towardbiodegradable capsules was increased since environmental aspects ofpolymers started to be discussed in the public and efforts were made toreduce environmental pollution.

Generally polyurethanes are prepared by reacting a polyisocyanate with apolyol component. Typical polyols employed in the preparation ofpolyurethanes are polyether polyols or polyester polyols. There is stilla demand for polyurethanes that are suitable as polymeric shell materialin microcapsules. For certain applications it would be advantageous thatsaid shell material apart from having good application properties isalso biodegradable.

WO 2006/044305 relates to an isocyanate-terminated prepolymercomposition obtained by reaction of methylene diphenylisocyanate with apolycaprolactone polyol. The obtained prepolymer is used in themanufacture of polyurethane or polyurea elastomers.

WO 2008/033224 relates to isocyanate-terminated polycaprolactonepolyurethane prepolymers obtained by reaction of toluene diisocyanateand a polyol composition. The obtained prepolymer can reacted with anamine chain extender resulting in polyurethane elastomers.

WO 03/061817 relates to substrates coated with polymers, containingmicrocapsules in the polymer layer, wherein the polymers includes forexample polyurethanes, polyurethaneureas, polyacrylonitriles orcopolymers of styrene.

U.S. Pat. No. 4,379,071 relates to a process for the production ofmicrocapsules, wherein a diol or polyol which has a molecular weight of400 to 10000 g/mol reacts with phosgene or a diisocyanate which containsat least two chloroformic acid esters or isocyanate groups per molecule.The resulting reaction product of those components is mixed with thedesired core material and a chain lengthening agent which is at leastbifunctional.

EP 0780154 relates to a process for preparing biodegradablemicrocapsules wherein the microcapsules are made by the additionreaction between polyamines, in particular aliphatic primary orsecondary di- or polyamines, and polyisocyanate components containing atleast one bifunctional isocyanate with an average of at least one esterand/or amide group in the main chain.

However, there continues to be a need for microcapsules, wherein thesize of the micropasules can be controlled in a wide range and that arecapable of releasing an encapsulated ingredient under controlledconditions. There is also a demand for microcapsules which have at leastone encapsulated hydrophobic component, wherein the microcapsules haveenhanced stability against leaking of the encapsulated components fromthe capsules. Delayed release of the encapsulated active ingredients forcrop protection, personal care compositions or pharmaceuticalcompositions, is also of interest.

It is an object of the present invention to provide a microcapsule,wherein the shell comprises a polymer containing polyurethane and/orpolyurea groups, which can be prepared by reactive microencapsulation,in particular by in situ radical polymerization, polyaddition orpolycondensation. It is a further object of the present invention toprovide such microcapsules wherein the shell of the microcapsules hasthe afore-mentioned desired properties and containing a hydrophobiccomponent as core material. Depending on the desired field ofapplication in one variant the microcapsules should be provided as a“normal” dispersion, comprising microcapsules containing at least onehydrophobic core material in an aqueous medium as the continuous phase.Further, it is an object of the present invention to providemicrocapsules for the use as or in a personal care composition, as or ina composition used for industrial or institutional or hospitaldisinfection, as or in a material protection composition, as or in apharmaceutical composition, as or in a plant protection composition, asor in home care products. Last but not least, it is an object of thepresent invention to provide a microcapsule compositions havingbiodegradable segments embedded in the capsule wall.

Surprisingly, these objects could be achieved by microcapsules, whereinthe core comprises at least one hydrohilic or at least one hydrophobiccomponent and wherein the shell of the microcapsules comprises polyureaand/or polyurethane linkages. In particular, the shell material of themicrocapsules according to the invention comprises apoly(ester-urethane) in polymerized form.

The present invention relates to microcapsule comprising a capsule coreand a polymeric shell, wherein the core essentially contains onlyhydrophobic components and the shell comprises in polymerized form

-   A) at least one poly(ester-urethane) containing at least 2    isocyanate groups, obtainable by reacting at least one    polyester-polyol containing at least 2 OH groups with at least one    polyisocyanate containing at least 2 NCO groups, and-   B1) at least one polymeric polyamine having a weight average    molecular weight of at least 300 g/mol and containing at least 3    amino groups reactive towards NCO groups,-   B2) optionally at least one compound different from B1) which    comprises at least 2 terminal groups which are reactive towards    isocyanate-groups, which are selected from OH, NHR, or SH, wherein R    is selected from hydrogen, alkyl, cycloalkyl or aryl.

The present invention further relates to microcapsule dispersion,comprising microcapsules wherein the capsule core contains essentiallyhydrophobic components, obtainable by

-   a) providing a premix (Ib) comprising the hydrophobic component(s)    to be encapsulated (Cb), optionally a hydrophobic medium that is    liquid at 20° C. and 1023 mbar different from (Cb), and at least one    component (A) as defined above and below, and-   b) mixing the premix (Ib) provided in step a) with an hydrophilic    medium comprising at least one hydrophilic protective colloid, at    least one component (B1) as defined which is defined above and    below, and reacting the resulting mixture to form microcapsules    dispersed in the hydrophilic medium.

The present invention further relates to a process for the preparationof the microcapsule dispersion, comprising microcapsules according tothe invention, wherein the capsule core contains essentially hydrophobiccomponents, obtainable by

-   a) providing a premix (Ib) comprising the hydrophobic component(s)    to be encapsulated (Cb), optionally a hydrophobic medium that is    liquid at 20° C. and 1023 mbar different from (Cb), and at least one    component (A) as defined above and below,-   b) mixing the premix (Ib) provided in step a) with an hydrophilic    medium comprising at least one hydrophilic protective colloid, at    least one component (B1) as defined above and below, and reacting    the resulting mixture to form microcapsules dispersed in the    hydrophilic medium.

The present invention further relates to a microcapsule obtained by theprocesses according to the invention. The present invention furtherrelates to microcapsules obtained by the processes according to theinvention in dry form. The present invention further relates to the useof microcapsules or microcapsules according to the invention or obtainedby the processes according to the invention in a personal carecomposition, or a home care composition, or a composition used forindustrial or institutional or hospital applications, or a materialprotection composition, or a pharmaceutical composition, or a plantprotection composition. The present invention further relates to the useof the microcapsules according to the invention or obtained by theprocesses according to the invention in a cosmetic composition, ahygiene composition, a composition for industrial or institutional orhospital cleaning or disinfection, laundry detergents, fabric softeners,dishwashing liquids, household cleaners, industrial cleaners, oilrecovery, adhesives, coatings, or constructions, or agro formulations.

The microcapsules according to the invention have the followingadvantages:

-   -   Small particle size and narrow particle size distribution    -   Good tightness and mechanical stability    -   Sprayable    -   Partially made out of biodegradable building blocks

The terms “biodegradation” or “biodegradability” are synonyms and meanin the sense of the invention that the polymers decompose in anappropriate and demonstrable period of time when exposed to the effectsof the environment. The degradation mechanism can be hydrolytic and/oroxidative, and is based mainly on exposure to microorganisms, such asbacteria, yeasts, fungi, and algae. An example of a method fordetermining biodegradability mixes the polymer with compost and storesit for a particular time. According to ASTM D5338, ASTM D6400, EN 13432,and DIN V 54900, CO₂-free air, by way of example, is passed throughripened compost during the composting process, and this compost issubjected to a defined temperature program. Biodegradability is definedhere by way of the ratio of the netto amount of CO₂ liberated from thespecimen (after deducting the amount of CO₂ liberated by the compostwithout the specimen) to the maximum possible amount of CO₂ liberated bythe specimen (calculated from the carbon content of the specimen). Evenafter a few days of composting, biodegradable polymers generally showmarked signs of degradation, for example fungal growth, cracking, andperforation.

In another method of determining biodegradability, the polymer isincubated with a certain amount of a suitable enzyme at a certaintemperature for a defined period, and then the concentration of theorganic degradation products dissolved in the incubation medium isdetermined. By way of example, by analogy with Y. Tokiwa et al.,American Chemical Society Symposium 1990, Chapter 12, “Biodegradation ofSynthetic Polymers Containing Ester Bonds”, the polymer can be incubatedfor a number of hours at from 30 to 37° C. with a predetermined amountof a lipase, for example from Rhizopus arrhizus, Rhizopus delemar,Achromobacter sp., or Candida cylindracea, and the DOC value (dissolvedorganic carbon) can then be measured on the reaction mixture freed frominsoluble constituents. For the purposes of the present invention,biodegradable polymers are those which after enzymatic treatment with alipase from Rhizopus arrhizus for 16 h at 35° C. give a DOC value whichis at least 10 times higher than that for the same polymer which has notbeen treated with the enzyme.

The term “functionality” represents, here and subsequently, the averagenumber of the respective functional groups per molecule or per polymerchain.

The term “dispersion” is a system of at least two phases, wherein one ofthese phases is the continuous phase and at least one phase isdispersed. Dispersion is a generic term, which encompasses e.g.emulsions, wherein the continuous phase is liquid and the dispersedphase is liquid, suspensions wherein the continuous phase is liquid andthe dispersed phase is solid, solid aerosole, wherein continuous phaseis gas and the dispersed phase is solid.

In the context of the present invention, the expression “alkyl”comprises straight-chain and branched alkyl groups. Suitable short-chainalkyl groups are, e.g. straight-chain or branched C₁-C₇ alkyl,preferably C₁-C₆ alkyl and particularly preferable C₁-C₄ alkyl groups.These include in particular methyl, ethyl, propyl, isopropyl, n-butyl,2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl,3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl,3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, and the like. Suitablelong-chain C₈-C₃₀ alkyl or C₈-C₃₀ alkenyl groups are straight-chain andbranched alkyl or alkenyl groups. In this connection, they arepreferably mainly linear alkyl residues, such as those also present innatural or synthetic fatty acids and fatty alcohols and also oxoalcohols, which, if appropriate, in addition can be mono-, di- orpolyunsaturated. These include, e.g., n-hexyl(ene), n-heptyl(ene),n-octyl(ene), n-nonyl(ene), n-decyl(ene), n-undecyl(ene),n-dodecyl(ene), n-tridecyl(ene), n-tetradecyl(ene), n-pentadecyl(ene),n-hexadecyl(ene), n-heptadecyl(ene), n-octadecyl(ene), n-nonadecyl(ene),and the like.

Cycloalkyl preferably represents C₅-C₈ cycloalkyl, such as cyclopentyl,cyclohexyl, cycloheptyl or cyclooctyl. Aryl comprises unsubstituted andsubstituted aryl groups and preferably represents phenyl, tolyl, xylyl,mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyland in particular phenyl, tolyl, xylyl or mesityl.

The volume average particle size can be measured by light scatteringmeasurements using a Malvern 2000S instrument and the Mie scatteringtheory.

Microcapsule

A first aspect of the invention relates to microcapsules per se.

One important parameter of the microcapsules of the invention is theshell weight of the capsules in relation to the total weight of thecapsules. It is expressed as percentage of the shell weight withreference to the total weight of the capsules (=encapsulated lipophiliccomponent+shell material).

The percentage of the shell weight with reference to the total weight ofthe capsules is of 5% to 40%, particularly 5% to 25%, and moreparticularly 10% to 20%.

The microcapsules of the microcapsule composition typically havecore/shell ratios (w/w) from 20:1 to 1:10, preferably from 10:1 to 5:1and in particular from 4:1 to 3:1.

A microcapsules of the microcapsule composition typically have the meanparticle size d(0.5) is from 0.5 μm to 50 μm, preferably from 0.7 μm to30 μm, and in particular from 1 μm to 10 μm.

Within the context of the present invention, the microcapsules have ashell that is prepared by reacting at least one poly(ester-urethane)containing isocyanate groups (A) with at least one compound (B)(=variant 1) or with at least one compound (B1) and optionally with atleast one compound (B2) (=variant 2), wherein compounds (B), (B1) and(B2) comprise terminal groups which are reactive towardisocyanate-groups, and optionally further components capable of beingincorporated into the shell. The reaction is a polyaddition between theisocyanate groups and a compound having at least one terminal groupwhich is reactive toward isocyanate group, and optional further groups,capable of reacting with NCO groups, which leads to the formation ofpolyurethane and/or polyurea linkages. The compounds B), B1) and B2)may, in addition to at least one primary or secondary amino group,contain at least one further group, capable of reacting with NCO groups,e.g. at least one OH group. Further components, capable of beingincorporated into the shell are in principle all compounds which containat least one active hydrogen atom per molecule. Reaction of NCO groupswith amine groups leads to the formation of urea groups. Reaction of NCOgroups with OH groups leads to the formation of urethane groups.Compounds containing only one active hydrogen atom per molecule lead toa termination of the polymer chain and can be employed as regulators.Compounds containing more than two active hydrogen atoms per moleculelead to the formation of branched polyureas.

The compounds which contain at least one active hydrogen atom permolecule are usually employed in a molar excess of active hydrogen atomsrelative to the NCO groups of the polyisocyanate. The amount ofcomponent B which is introduced is usually in a molar excess, relativeto the stoichiometric amount needed to convert the free isocyanategroups. Suitable polyesters, polyisocyanates, polyfunctional amines, andoptional components that take part in the polyaddition orpolycondensation, e.g. reaction, hydrohilic or hydrophobic components,protective colloids, stabilizing agent and further additives, arementioned below.

Component (A): Poly(Ester-Urethane) Containing Isocyanate Groups

The term “polyurethane” comprises, in the context of this invention, notonly polymers whose repeat units are bonded to one another via urethanegroups but very generally polymers which can be obtained by reaction ofat least one polyisocyanate with at least one compound exhibiting atleast one group which is reactive with regard to isocyanate groups.These include polymers whose repeat units, in addition to urethanegroups, are also connected by urea, allophanate, biuret, carbodiimide,amide, uretonimine, uretdione, isocyanurate or oxazolidone(oxazolidinone) groups (see, for example, Plastics Handbook, Saechtling,26th edition, p. 491 seq., Carl Hanser Verlag, Munich, 1995). The term“polyurethane” comprises in particular polymers comprising urethaneand/or urea groups.

The poly(ester-urethane) used according to the invention is preferably areaction product of at least one polyester-polyol containing at least 2hydroxyl groups (OH groups) with at least one polyisocyanate containingat least 2 isocyanate groups (NCO groups). The poly(ester-urethane) usedaccording to the invention contains at least 2 isocyanate groups thatare capable of reacting with complementary groups containing activehydrogen atoms.

The polyester-polyol typically has a OH functionality of greater than 1,preferably from 2 to 6, more preferably from 2 to 5, e.g. 2, 3 or 4.

In a special embodiment, the polyester-polyol is selected from aliphaticpolyester-polyols.

The polyester-polyol preferably has a weight-average molecular weight offrom 200 to 3000, more preferably from 205 to 2000, e.g. from 240 to1240 g/mol.

The polyester-polyol typically has a hydroxyl value of from 20 to 800 mgKOH/g, preferably 30 to 600 mg KOH/g, more preferably 40 to 550 mgKOH/g.

The polyester-polyol typically has an acid number of from 0 to 15,preferably from 0 to 10, in particular 0 to 5.

The polyester-polyol typically has a viscosity at 60° C. of from 40 to1100 mPa·s preferably from 100 to 500 mPa·s.

The polyester-polyol typically has at least 2, preferably 4, inparticular 7 repeating units connected by ester groups.

Suitable polyesters-polyols include but not limited, for example,polyesters comprising in polymerized form trimethylene carbonate,ε-caprolactone, p-dioxanone, glycolide, lactide, 1,5-dioxepan-2-one, orthe poyesters polybutylene adipate, polyethylene adipate, polyethyleneterephthalate, and combinations thereof. In embodiments the polyestermay comprise in polymerized form lactide, glycolide, ε-caprolactone,and/or combinations thereof.

Suitable polyester-polyols for the preparation of microcapsulesaccording to the invention exhibit two or more than two (e.g., 3, 4, 5,6, and the like) hydroxyl groups. In this connection, the hydroxylgroups can also be partially or completely replaced by mercapto groups.

Preferably, the polyester-polyol used for the preparation of the atleast one poly(ester-urethane)

A) contains in polymerized form(a1) at least one polyol, and(a2) at least one polycarboxylic acid, and/or(a3) at least one hydroxycarboxylic acid.

More preferably, the polyester-polyol used for the preparation of the atleast one poly(ester-urethane) A) contains in polymerized form at leastone polyol (a1), and at least one hydroxycarboxylic acid (a3).

Suitable polyols (a1) are diols, polyols containing more than 2 OHgroups and mixtures thereof.

The term “polyols containing more than 2 OH groups” usually refers topolyols having at least 3 OH groups.

Suitable polyols containing more than 2 OH groups, and suitable polyolshaving at least 3 OH groups are triols and high molecular weight polyols(also called polymeric polyols), wherein triols are preferred. Preferredpolyols (a1) are diols and triols, wherein triols are preferred. Inparticular polyols (a1) are selected from glycerol(propane-1,2,3-triol), butane-1,2,4-triol, n-pentane-1,2,5-triol,n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol,(1,1,1)-trimethylolpropane (TMP) and trimethylolbutane.

Suitable diols are straight-chain and branched aliphatic andcycloaliphatic alcohols with generally approximately 2 to 30, preferablyapproximately 2 to 20, carbon atoms. These include 1,2-ethanediol,1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol,1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol,1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol,1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol,2-methyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, pinacol,2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol,dipropylene glycol, tripropylene glycol, polyalkylene glycols,cyclopentanediols, cyclohexanediols, and the like.

Suitable triols are, e.g., glycerol (propane-1,2,3-triol),butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol,n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, (1,1,1)-trimethylolpropane(TMP) and trimethylolbutane.

Suitable triols are furthermore the triesters of hydroxycarboxylic acidswith trivalent alcohols. Preferably, in this connection, they aretriglycerides of hydroxycarboxylic acids, such as, e.g., lactic acid,hydroxystearic acid and ricinoleic acid. Naturally occurring mixturescomprising hydroxycarboxylic acid triglycerides, in particular castoroil, are also suitable.

Suitable polyols of higher valency are, e.g., sugar alcohols and theirderivatives, such as erythritol, pentaerythritol, dipentaerythritol,threitol, inositol and sorbitol. Reaction products of the polyols withalkylene oxides, such as ethylene oxide and/or propylene oxide, are alsosuitable.

Relatively high molecular weight polyols (also called herein polymericpolyols) with a number-average molecular weight in the range ofapproximately 400 to 6000 g/mol, preferably 500 to 4000 g/mol, can alsobe used. These include, e.g., polyalkylenglycoles (PEGs) such aspolyethylene glycol (PEG) diol, and a copolymer diol of polyethyleneglycol (PEG) diol and polypropylene glycol (PPG) diol or polybutyleneglycol (PBG) diol. These furthermore include polytetrahydrofurandiolswhich can be obtained, e.g., by acid-catalyzed polymerization oftetrahydrofuran.

These furthermore include polylactonepolyols which are obtainable(preferably can be obtained) e.g. by ring-opening additionpolymerization of a hydroxyl-terminated compound (e.g. diol or triol)and a monomer that includes a lactone ring (e.g., ε-caprolactone orβ-methyl-δ-valerolactone).

These furthermore include polylactonediols which can be obtained, e.g.,by polylactonediol obtained by ring-opening addition polymerization of ahydroxyl-terminated compound (e.g., polyol or polyester polyol) and amonomer that includes a lactone ring (e.g., ε-caprolactone orβ-methyl-δ-valerolactone).

These furthermore include polyesterols based on aliphatic,cycloaliphatic and/or aromatic di-, tri- and/or polycarboxylic acidswith di-, tri- and/or polyols, and also the polyesterols based onlactone. These furthermore include polyetherols which can be obtained,e.g., by polymerization of cyclic ethers or by reaction of alkyleneoxides with an initiator molecule. These furthermore also includeconventional polycarbonates with terminal hydroxyl groups known to aperson skilled in the art which can be obtained by reaction of the diolsdescribed above or also bisphenols, such as bisphenol A, with phosgeneor carbonic diesters. α,ω-Polyamidols, poly(methyl (meth)acrylate)α,ω-diols and/or poly(butyl (meth)acrylate α,ω-diols, such as, e.g.,MD-1000 and BD-1000 from Goldschmidt, are also suitable.

In a preferred embodiment the poly(ester-urethane) A) is obtainable byreacting at least one polylactonpolyol containing at least 2 OH groupswith at least one polyisocyanate containing at least 2 NCO groups. Inother words, the polyester-polyol used for the preparation of thepoly(ester-urethane) A) is a polylactonpolyol.

Preferably, the polylactonpolyol contains 2 or 3 OH groups. Inparticular, the polylactonpolyol is a polycaprolactonediol or apolycaprolactontriol.

Preferably, polylactonpolyol is a polycaprolactonediol or apolylactontriol having a number-average molecular weight of from 200 to5000 g/mol, more preferably 250 to 3000 g/mol.

Preferably, the polyester-polyol is selected from compounds of theformulae (1), (2), (3), (4), (5) and mixtures thereof

-   wherein-   R^(a) is a divalent aliphatic or cycloaliphatic radical,-   R^(b) is a trivalent aliphatic or cycloaliphatic radical-   l, m and n are independently an integer of 1 to 100,-   with the proviso that-   in the formula (1) n is an integer of 2 to 100,-   in the formula (2) n+m is an integer of 2 to 100,-   in the formula (3) n is an integer of 2 to 100,-   in the formula (4) n+m is an integer of 2 to 100,-   in the formula (5) n+m+l is an integer of 2 to 100.

Suitable radicals R^(a) are linear or branched C₁-C₁₀-alkylene groupsthat are optionally interrupted by 1, 2, 3, 4 or 5 non-neighboringoxygen atoms and C₃-C₂₀-cycloaliphatic radicals having 3 to 10 ringcarbon atoms.

Suitable radicals R^(b) are linear or branched C₁-C₁₀-alkantriyl groupsthat are optionally interrupted by 1, 2, 3, 4 or 5 non-neighboringoxygen atoms.

Preferred radicals R^(a) are methylene, 1,2-ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene,1,1-dimethyl-1,2-ethylene, 1,2-dimethyl-1,2-ethylene, 1,5-pentylene,1,6-hexylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene, —CH₂—O—CH₂,—CH₂—CH₂—O—CH₂—CH₂— and —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—.

More preferred radicals R^(a) are 1,2-ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene,—CH₂—CH₂—O—CH₂—CH₂— and —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—.

Preferred radicals R^(b) are

More preferably, the polyester-polyol is selected from compounds of theformulae (2), (5) and mixtures thereof, wherein compounds of theformulae (5) are in particular preferred.

In particular, the polyester-polyol is selected from compounds of theformulae (2), (5) and mixtures thereof (in particular from formula (5)),wherein

-   R^(a) is selected from linear or branched C₁-C₁₀-alkylene group and    C₃-C₂₀-cycloaliphatic radicals having 3 to 10 ring carbon atoms,-   R^(b) is a linear or branched C₁-C₁₀-alkantriyl group,-   l, m and n are independently an integer of 1 to 100,-   with the proviso that-   in the formula (2) n+m is an integer of 2 to 100,-   in the formula (5) n+m+l is an integer of 2 to 100.

In one preferred embodiment, the polyester-polyol containing at least 2OH groups is obtainable (preferably it is obtained) by reaction of atleast one diol and/or polyalkylenglycol with at least one polylacton, inparticular the polyester-polyol containing at least 2 OH groups isobtained by reaction of diethylenglycol and poly-s-caprolacton.

In another preferred embodiment, the polyester-polyol containing atleast 2 OH groups is obtainable (preferably it is obtained) by reactionof at least one polyol having at least 3 OH groups with at least onepolylacton, in particular the polyester-polyol containing at least 2 OHgroups is obtained by reaction of trimethylolpropane and/or glycerol andpoly-s-caprolacton.

In another preferred embodiment, the polyester-polyol containing atleast 2 OH groups is obtainable (preferably it is obtained) by reactionof at least one polyol having at least 3 OH groups selected fromglycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol,n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol,(1,1,1)-trimethylolpropane and trimethylolbutane with at least onepolylacton.

One embodiment relates to microcapsules as defined above and below,wherein the polyester-polyol containing at least 2 OH groups isobtainable (preferably it is obtained) by reaction of at least one dioland/or polyalkylenglycol with at least one polylacton.

Another embodiment relates to microcapsules as defined above and below,wherein the polyester-polyol containing at least 2 OH groups isobtainable (preferably it is obtained) by reaction of at least onepolyol having at least 3 OH groups and/or polymeric polyol having atleast 3 OH with at least one polylacton.

Suitable non-limiting examples of commercially availablepolyester-polyols are Caproper™ PD4-05 (a polycaprolactonediol), theLUPRAPHEN® brands available from BASF SE (e.g. Lupraphen 6601/3 adifunctional, aliphatic polyester-polyol) and (Tri-iso) Capa 3031available from Perstorp.

One isocyanate group is supposed to react with a terminal hydroxyl groupof the polyester-polyol and whilst the other isocyanate group of thediisocyanate is preserved. To avoid polymerization of high molecularweight chains, at least the mole equivalent of diisocyanate compared tohydroxyl groups has to be used in the reaction mixture. Once thefunctionalization is completed poly(ester-urethane)-diisocyanates areobtained as macromonomers.

The reaction progress is monitored by the frequent determination of theisocyanate content of the solution. The functionalization is completeafter the conversion of 50% of the isocyanate groups. The isocyanate(NCO) content is declared in grams of NCO per 100 g reaction mixture.

Isocyanates are N-substituted organic derivatives (R—N═C═O) of isocyanicacid (HNCO) tautomeric in the free state with cyanic acid. Organicisocyanates are compounds in which the isocyanate group (—N═C═O) isbonded to an organic radical. Polyfunctional isocyanates are compoundswith two or more (e.g. 3, 4, 5, etc.) isocyanate groups in the molecule.

Preferably, the polyisocyanate according to the incention comprises atleast one difunctional isocyanate. In a special embodiment, thepolyisocyanate is exclusively selected from difunctional isocyanates,the allophanates, isocyanurates, uretdiones or carbodiimides ofdifunctional isocyanates and mixtures thereof.

In general, suitable polyisocyanates are all aromatic, alicyclic andaliphatic polyisocyanates, provided they have at least two reactiveisocyanate groups. Preferably, the polyisocyanate component has anaverage content of 2 to 4 NCO groups. Preference is given to usingdiisocyanates, i.e. esters of isocyanic acid with the general structureO═C═N—R′—N═C═O, where R′ is an aliphatic, alicyclic or aromatic radical.Suitable polyisocyanates are chosen from compounds with 2 to 5isocyanate groups, isocyanate prepolymers with an average number of from2 to 5 isocyanate groups and mixtures thereof. These include, forexample, aliphatic, cycloaliphatic and aromatic di-, tri- and higherpolyisocyanates.

Preferably, the polyisocyanates comprise only a minor amount ofcompounds with aromatic rings. In particular, not more than 5 wt % ofthe polyisocyanates, based on the complete amount of thepolyisocyanates, comprises an aromatic ring. In a special embodiment thepolyisocyanate is selected only from aliphatic polyisocyanates. The term“aliphatic polyisocyanate” in the sense of the invention encompassesalso non-aromatic cyclic polyisocyanates, e.g. isophorone diisocyanate.

Preferably, the polyisocyanate is selected from ethylene diisocyanate,tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate,hexamethylene diisocyanate(1,6-diisocyanatohexane, HDI), octamethylenediisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,tetradecamethylene diisocyanate,4-isocyanatomethyl-1,8-octamethylenediisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane,1,6-diisocyanato-2,4,4-trimethylhexane, 2,3,3-trimethylhexamethylenediisocyanate, tetramethylhexane diisocyanate, lysine diisocyanate,isophorone diisocyanate(=3-Isocyanatmethyl-3,5,5-trimethylcyclohexylisocyanat,1-Isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexan, IPDI),1,4-cyclohexylene diisocyanate, 1,3-cyclohexylene diisocyanate,1,2-cyclohexylene diisocyanate, 4,4′-di(isocyanatocyclohexyl)methane, or2,4′-di(isocyanatocyclohexyl)methane,1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane,1-methyl-2,4-diisocyanatocyclohexane,1-methyl-2,6-diisocyanatocyclohexane, 1,3-phenylene diisocyanate,1,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate andisomer mixtures thereof, 1,5-naphthylene diisocyanate, 2,4′- and4,4′-diphenylmethane diisocyanate (MDI), mixtures of diphenylmethanediisocyanates and more highly polycyclic homologs of diphenylmethanediisocyanate (polymeric MDI), hydrogenated 4,4′-diphenylmethanediisocyanate (H12MDI), xylylene diisocyanate (XDI), tetramethylxyloldiisocyanate (TMXDI), 4,4′-dibenzyl diisocyanate,4,4′-diphenyldimethylmethane diisocyanate, di- andtetraalkyldiphenylmethandiisocyanates,triphenylmethane-4,4′,4″-triisocyanate, dimer fatty acid diisocyanates,chlorinated and brominated diisocyanates,4,4′-diisocyanatophenylperfluoroethane,tetramethoxybutane-1,4-diisocyanate, phosphorus-containingdiisocyanates, sulfur-containing diisocyanares, anionically modifiedpolyisocyanates, polyethylene oxide-containing isocyanate, oligomers ofthe afore-mentioned polyisocyanates that contain urethane, allophanate,isocyanurate, uretdione, carbodiimide or biuret groups, and mixturesthereof.

Suitable chlorinated and brominated polyisocyanates comprisepolyisocyanates with reactive halogen atoms. Preferably, the chlorinatedand brominated polyisocyanate is selected from 1-chloromethylphenyl2,4-diisocyanate, 1-bromomethylphenyl 2,6-diisocyanate,3,3-bischloromethyl ether 4,4′-diphenyldiisocyanate. Suitablesulfur-containing polyisocyanates are obtained, for example, by reacting2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol ordihydroxydihexyl sulfide.

The polyisocyanate preferably comprises at least one aliphaticdiisocyanate, selected from tetramethylene diisocyanate,1,5-pentamethylene diisocyanate, hexamethylenediisocyanate(1,6-diisocyanatohexane), octamethylene diisocyanate,decamethylene diisocyanate, dodecamethylene diisocyanate,tetradecamethylene diisocyanate, lysine diisocyanate, trimethylhexanediisocyanate, tetramethylhexane diisocyanate,1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,1,2-diisocyanatocyclohexane, 4,4′-di(isocyanatocyclohexyl)methane,2,4′-di(isocyanatocyclohexyl)methane, isophorone diisocyanate,1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane,2,4-diisocyanato-1-methylcyclohexane and2,6-diisocyanato-1-methylcyclohexane.

The polyisocyanate preferably comprises at least one polyisocyanate,selected from hexamethylene diisocyanate, tetramethylene diisocyanate,isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 2,4- and2,6-toluylene diisocyanate and isomer mixtures thereof, 2,4′- and4,4′-diphenylmethane diisocyanate, the biurets, allophanates and/orisocyanurates of the aforementioned polyisocyanates, anionicallymodified polyisocyanates, and mixtures thereof.

Preferably, polyisocyanates are selected from hexamethylenediisocyanate, tetramethylene diisocyanate, isophorone diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, 2,4- and 2,6-toluylenediisocyanate and isomer mixtures thereof, 2,4′- and 4,4′-diphenylmethanediisocyanate and isomer mixtures thereof, the biurets, allophanatesand/or isocyanurates of the afore-mentioned polyisocyanates or mixturesthereof.

In particular, the polyisocyanates are selected from hexamethylenediisocyanate, isophorone diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, the isocyanurate of hexamethylenediisocyanate or mixtures thereof.

Especially, the polyisocyante is isophorone diisocyanate.

Component B, (B1) and (B2)

The shell comprises in polymerized form

-   B1) at least one polymeric polyamine (B1) having a weight average    molecular weight of at least 300 g/mol and containing at least 3    amino groups reactive towards NCO groups, and-   B2) optionally at least one compound (B2), which is different from    B1) and which comprises at least 2 terminal groups which are    reactive towards isocyanate-groups, which are selected from OH, NHR,    or SH, wherein R is selected from hydrogen, alkyl, cycloalkyl or    aryl.

Suitable polymeric polyamines (B1) are in principle linear or branchedpolymers that have at least two primary or secondary amino groups.Additionally, these polymers can have tertiary amino groups in thepolymer chain.

Preference is given to polymeric polyamines having a weight-averagemolecular weight of at least 300 g/mol. More preferred are polymericpolyamines having a weight-average molecular weight of from 350 to 3000,in particular from 375 to 2500, especially from 400 to 2000, moreespecially from 500 to 1500. Furthermore, polymeric polyamines typicallyhas at least 3, preferably 4, in particular 5 repeating units.

The polymeric polyamine is preferably selected frompolyaminosaccharides, polyamidoamines, polyesteramines, polyetheramines,polyvinylamines, polyaminoacids polyaminoacids, and combinationsthereof.

Preferably, the polymeric polyamine comprises a polyamidoamines, inparticular polylysine. More preferably, the polymeric polyaminecomprises polylysine which has a average molecular weight from of 300 to4000 g/mol, preferably from 500 to 3000 g/mol.

Preferred polyesteramines are in the context of the present invention,very generally polymeric compounds exhibiting ester groups and aminogroups in the chain, amino groups not being part of an amide group. Inprinciple, at least divalent compounds exhibiting one amino group,preferably no longer available for a subsequent reaction, and at leasttwo additional functional groups, capable of an addition or condensationreaction, can be used. These include, for example,N-alkyl-N-(hydroxyalkyl)aminoalkanecarboxylic acids and carboxylic acidderivatives, N,N-di(hydroxyalkyl)aminoalkanecarboxylic acids andcarboxylic acid derivatives, N-alkyl-N-(aminoalkyl)aminoalkanecarboxylicacids and carboxylic acid derivatives,N,N-di(aminoalkyl)aminoalkanecarboxylic acids and carboxylic acidderivatives, and the like. In addition to these monomers, thepolyesteramines used according to the invention can comprise additionalpolyfunctional compounds incorporated exhibiting two or more than two(e.g., 3, 4, 5, 6, and the like) functional groups. These include theabove-described polycarboxylic acids, polyfunctional amines,polyfunctional alcohols and polyfunctional aminoalcohols, reference towhich is made here in their entirety.

Preferred polyamidoamines are dendrimer which is made of repetitivelybranched subunits of amide and amine functionality. Preferredpolyamidoamines are polylysine, which is homopolymers from lysine. It isprepared from amino acid lysine, which contains two amino groups, one atthe α-carbon and one at the ε-carbon. Either can be the location ofpolymerization, resulting in α-polylysine or ε-polylysine. Preference isgiven to polylysine which have a average molecular weight from of 300 to4000 g/mol, preferably from 400 to 3000 g/mol, more preferably, 500 to1500 g/mol. Furthermore, polylysine according to the invention has atleast 3, preferably 4, in particular 5 repeating units.

Preferred polyaminosaccharides are sugar molecule in which a hydroxylgroup has been replaced with an amine group. Preferred are chitosancomposed of randomly distributed 13-(1-4)-linked D-glucosamine(deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit).

Preferred polyvinylamines (polyaminoethylene) are known productsobtained by homo- or copolymerization of N-vinylformamide followed bypartial or complete hydrolysis.

Preferred polyetheramines are the reaction products of at least onepolyol with at least one C₂-C₁₈ alkylene oxide, to form an alkoxylatedpolyol and aminating the alkoxylated polyol with ammonia.

Preferred polyamino acids usually consist of repeating units of aminoacids, wherein the homopolyamino acid is made from up of a single aminoacid as a repeating unit, and the co-polyamino acid is a polymer madefrom at least two or more different amino acids as repeating units.Polyamino acids contain both an amino and a carboxylic acid functionalgroup. Preferred polyamino acids are selected from the group consistingof poly-D,L-ornithine, poly-D,L-homoarginine, poly-D,L-arginine,poly-D,L-glutamic acid, poly-D,L-glutamic acid, poly-D,L-glutamic acid,poly-D,L-aspartic acid.

Preferred are also polyethyleneimines, which are selected from the groupconsisting of diethylenetriamine, triethylenetetramine,tetraethylenepentamine, ethylenepropylenetriamine, trisaminopropylamineand higher polyethyleneimines. Preferably the polyethyleneimines have anumber-average molecular weight of at least 300 g/mol, preferably from400 to 3000 or 450 to 2500 g/mol and in particular from 450 to 2000g/mol. In a preferred embodiment, the polymeric polyamine is selectedfrom polyethyleneimines having a weight average molecular weight of atleast 300 g/mol. Suitable polyethylenimines contain the following repeatunits

whereinx is from 8 to 1500, preferably from 10 to 1000;y is from 0 to 10, preferably from 0 to 5, especially 0;z is 2+y.

Preferred polyethyleneimines are linear polyethyleneimines, wherein x isfrom 8 to 1500, y is 0 and z is 2. Preferred commercially availablepolyethylenimines are sold by BASF SE under the trademark Lupasol™ andthe Jeffamine trademarks from Huntsman, particularly Lupasol™ PR8515.

If the core essentially contains only hydrophobic components, preferenceis given to hexamethylene diamine, ethylenediamine,N-ethylethylenediamine, N,N′-diethylethylenediamine, diethylenetriamine,tetraethylene pentamine, spermine, spermidine, polyvinylamines,polyetheramines, polyesteramines and polyamidoamines. Suitable compounds(B2) are polyfunctional alcohols, polyfunctional amines, or mixturesthereof. Preferably, the compound (B2) comprises a polyfunctionalalcohol.

In the sense of the invention, the term polyfunctional alcohol denotesalcohols that comprise at least two groups capable of reacting with NCOgroups, wherein at least one of the groups capable of reacting with NCOgroups is a OH group. When the polyfunctional alcohol contains only oneOH group, it will contain one or more additional functional groups thatare capable of reacting with NCO groups in a polymerisation reaction.Suitable are in principle active hydrogen atom containing groups. Thegroups of the polyfunctional alcohol that are reactive toward NCO groupsare preferably chosen from hydroxyl groups and primary and secondaryamino groups.

Suitable polyfunctional alcohols according to the exhibit two or morethan two (e.g., 3, 4, 5, 6, and the like) hydroxyl groups. In thisconnection, the hydroxyl groups can also be partially or completelyreplaced by mercapto groups.

Suitable diols are straight-chain and branched aliphatic andcycloaliphatic alcohols with generally approximately 2 to 30, preferablyapproximately 2 to 20, carbon atoms. These include 1,2-ethanediol,1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol,1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol,1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol,1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol,2-methyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, pinacol,2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol,dipropylene glycol, tripropylene glycol, polyalkylene glycols,cyclopentanediols, cyclohexanediols, and the like.

Suitable triols are, e.g., glycerol, butane-1,2,4-triol,n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol,n-hexane-1,2,5-triol, trimethylolpropane and trimethylolbutane. Suitabletriols are furthermore the triesters of hydroxycarboxylic acids withtrivalent alcohols. Preferably, in this connection, they aretriglycerides of hydroxycarboxylic acids, such as, e.g., lactic acid,hydroxystearic acid and ricinoleic acid. Naturally occurring mixturescomprising hydroxycarboxylic acid triglycerides, in particular castoroil, are also suitable. Suitable polyols of higher valency are, e.g.,sugar alcohols and their derivatives, such as erythritol,pentaerythritol, dipentaerythritol, threitol, inositol and sorbitol.Reaction products of the polyols with alkylene oxides, such as ethyleneoxide and/or propylene oxide, are also suitable. Relatively highmolecular weight polyols with a number-average molecular weight in therange of approximately 400 to 6000 g/mol, preferably 500 to 4000 g/mol,can also be used.

These include, e.g., polyesterols based on aliphatic, cycloaliphaticand/or aromatic di-, tri- and/or polycarboxylic acids with di-, tri-and/or polyols, and also the polyesterols based on lactone. Thesefurthermore include polyetherols which can be obtained, e.g., bypolymerization of cyclic ethers or by reaction of alkylene oxides withan initiator molecule. These furthermore also include conventionalpolycarbonates with terminal hydroxyl groups known to a person skilledin the art which can be obtained by reaction of the diols describedabove or also bisphenols, such as bisphenol A, with phosgene or carbonicdiesters. α,ω-Polyamidols, poly(methyl (meth)acrylate) α,ω-diols and/orpoly(butyl (meth)acrylate α,ω-diols, such as, e.g., MD-1000 and BD-1000from Goldschmidt, are also suitable.

In the sense of the invention, the term polyfunctional amine denotesamines that comprise at least two groups capable of reacting with NCOgroups, wherein at least one of the groups capable of reacting with NCOgroups is a primary or secondary amino group. When the polyfunctionalamine contains only one primary or secondary amino group, it willcontain one or more additional functional groups that are capable ofreacting with NCO groups in a polymerisation reaction. Suitable are inprinciple active hydrogen atom containing groups. The groups of thepolyfunctional amines that are reactive toward NCO groups are preferablychosen from hydroxyl groups and primary and secondary amino groups.

The polyfunctional amine is preferably selected from diamines,aminoalcohols, polymeric polyamines, guanidines, melamines, urea,hydrazines and mixtures thereof. When the compound (B2) comprises apolyfunctional amine which is a polymeric polyamines, the polymericpolyamine is different from the compound (B1).

Suitable diamines are, for example, 1,2-ethylenediamine,1,3-propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane(cadaverine), 1,6-diaminohexane, 1,3-diamino-1-methylpropane,1,4-diaminocyclohexane, piperazin, N-ethylethylenediamine,N,N′-diethylethylenediamine and mixtures thereof. Suitable amines whichhave at least two primary or secondary amino groups are, for examplediethylenetriamine, tetraethylene pentamine, spermine, spermidine andmixtures thereof.

Suitable amino alcohols are, for example, 2-aminoethanol,2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol, etc.

In a special embodiment of the invention the polymeric shell materialshows biodegradability.

In a preferred embodiment for providing a biodegradable polymeric shellmaterial the poly(ester-urethane) A) is prepared by reacting at leastone polycaprolactonediol or a polylactonetriol having a number-averagemolecular weight of from 250 to 3000 g/mol with at least onepolyisocyanate containing at least 2 NCO groups.

Core Material

Suitable hydrophobic components are mentioned in detail below.

In the sense of the invention, the term “hydrophobic component” isunderstood in a broad sense. It encompasses a single hydrophobiccomponent, a mixture comprising at least two hydrophobic components anda solution of at least one hydrophobic solid compound in a liquidhydrophobic compound.

The hydrophobic components used according to the invention have only alimited solubility in water. The solubility of the hydrophobiccomponents (e.g. the pesticide) in water at 20° C. and 1013 mbar ispreferably ≤10 mg/mL, more preferably ≤5 mg/mL, in particular ≤3 mg/mL.

The term “the core essentially contains only hydrophobic components”usually means that the core contains at least 80 wt %, preferably atleast 90 wt %, more preferably at least 95 wt %, and in particular atleast 98 wt % of the hydrophobic components.

In a special embodiment of the invention, the microcapsules containsubstantially no solvent in the core. According to the process of theinvention, it is possible to prepare a microcapsule composition, whereinthe encapsulated cores are composed entirely of hydrophobic componentsand no solvents. Solvent-free encapsulated hydrophobic components may beemployed, in particular, when the hydrophobic components making up thecore material are liquid under the conditions used for the preparationof the microcapsules.

Preferably, at least 60% by weight, more preferably at least 70% byweight, in particular at least 80% by weight and especially at least 90%by weight of hydrohobic components, based on the total weight of thehydrophobic components, have a solubility in water at 20° C. and 1013mbar of ≤10 mg/mL, particularly ≤5 mg/mL, and more particularly ≤3mg/mL.

The microcapsules contain one or more hydrophobic components.Preferably, the amount of the hydrophobic components (e.g. thepesticide) is in a range of from 5 to 97% by weight, more preferably 10to 95% by weight, in particular 25 to 93% by weight, based on the totalweight of the microcapsules. In a special embodiment, the amount of thehydrophobic components (e.g. the pesticide) is in a range of from 70 to98% by weight, based on the total weight of the microcapsules.

Advantageously, a large amount of hydrophobic components can beencapsulated in the microcapsules of the invention despite therelatively low shell weight. Preferably, the ratio of the total weightof the hydrophobic components to total weight of the shell material isin a range of from 60% to 95% by weight, more preferably 75% to 80% byweight, and more particularly 80% to 88% by weight.

In another form the core-shell ratio (w/w) of the microcapsules is 20:1to 1:10, preferably 10:1 to 5:1 and in particular 4:1 to 3:1. In apreferred form the core-shell ratio (w/w) of the microcapsules is 20:1to 1:1, preferably 10:1 to 2:1 and in particular 6:1 to 3:1.

The core-shell weight ratio may be obtained by weighing an amount ofcapsules that have been previously washed with water and separated byfiltration. The core is then extracted by solvent extraction techniquesto give a core weight. The shell weight is obtained from simple massbalance taking into account the initial amount of encapsulatingmaterials in weight %.

Hydrophobic components that are used can be various organic substances.In particular, the hydrophobic component is selected from activeingredients and auxiliaries for cosmetics (e.g. hair and skincosmetics), pharmaceuticals, hygiene compositions, detergents, cleaningagents, textile treatment compositions, etc., compositions used forindustrial or institutional or hospital applications, materialprotection compositions or plant protection compositions.

Active ingredients are substances which generally develop an effect evenat low concentration, e.g. a cosmetic effect on skin and/or hair, apharmacological effect in an organism, a plant protecting effect, acleaning and/or disinfecting effect, a modification of a textilesubstance, e.g. a crease-free finishing, and effect substances whichimpart a certain property to living things or inanimate substrates, forexample colors for make-up, mascara, etc.

Preferably, the hydrophobic component is selected from oil bodies,UV-filters, organic compounds biocides, dyes, emollients, vitamins,cosmetically active ingredients, pharmaceutically active ingredients,cosmetically and pharmaceutically acceptable auxiliaries, detergents,anti-oxidants, perfumes and fragrances or mixtures thereof.

In one embodiment the hydrophobic component of the microcapsule ormicrocapsule dispersion as defined above is selected from UV-filters,organic compounds, biocides, dyes, emollients, vitamins, cosmeticallyactive ingredients, pharmaceutically ingredient, detergent composition,anti-oxidant agents, fragrances or mixtures thereof.

A first class of hydrophobic components that can be encapsulated are oilbodies.

Preferably, the hydrophobic components comprise at least one oil bodycapable to dissolve the polyisocyanates (component (A)). Morepreferably, these oil body are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should an oil body notensure adequate solubility of the polyisocyanates, there is the optionof overcoming this disadvantage by using suitable solubility promoters.

The term oil body in the sense of the invention means vegetable oils,modified vegetable oils, synthetic (tri)glycerides, fatty acid alkylesters, fatty acid alkyl esters based on said C₆-C₂₂ fatty acids,mineral oils, silicone oils, hydrocarbons, saturated or unsaturatedC₆-C₃₀-fatty acids, aromatic compounds, waxes, polymers, Guerbetalcohols based on fatty alcohols, esters of linear C₆-C₂₂-fatty acidsand mixtures thereof. Preferred oil bodies are vegetable oils, modifiedvegetable oils, synthetic (tri)glycerides, fatty acid alkyl esters,fatty acid alkyl esters based on said C₆-C₂₂ fatty acids, mineral oils,hydrocarbons, saturated or unsaturated C₆-C₃₀-fatty acids, aromaticcompounds, esters of linear C₆-C₂₂-fatty acids and mixtures thereof.

Preferred oils are cosmetical acceptable oils like caprylic/caprictriglyceride, myristyl myristate, cetyl oleate.

Within the context of the present invention, preferred oil bodies areGuerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to10, carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear orbranched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylicacids with linear or branched C₆-C₂₂-fatty alcohols, such as e.g.myristyl myristate, myristyl palmitate, myristyl stearate, myristylisostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetylmyristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyloleate, cetyl behenate, cetyl erucate, stearyl myristate, stearylpalmitate, stearyl stearate, stearyl isostearate, stearyl oleate,stearyl behenate, stearyl erucate, isostearyl myristate, isostearylpalmitate, isostearyl stearate, isostearyl isostearate, isostearyloleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleylpalmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleylbehenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenylstearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucylisostearate, erucyl oleate, erucyl behenate and erucyl erucate.

A further class of hydrophobic components that can be encapsulated areUV filters. Preferably, the hydrophobic components comprise at least oneUV filters capable to dissolve the polyisocyanates (component (A)). Morepreferably, these UV-filters are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should an UV filter notensure adequate solubility of the polyisocyanates, there is the optionof overcoming this disadvantage by using suitable solubility promoters.

Typical hydrobhobic UV filters are UV-A filters, UV-B filters orbroad-spectrum UV A/B filters are, for example, 3-benzylidenecamphor or3-benzylidenenorcamphor and derivatives thereof, e.g.3-(4-methylbenzylidene)-camphor,3-(4′-trimethylammonium)benzylidenebornan-2-one methylsulfate (MexorylSO),3,3′-(1,4-phenylenedimethine)bis(7,7-dimethyl-2-oxobicycle-[2.2.1]heptane-1-methanesulfonicacid) and salts (Mexoryl SX), 3-(4′-sulfo)benzylidenebornan-2-one andsalts (Mexoryl SL), polymer of N-{(2 and4)-[2-oxoborn-3-ylidene)-methyl}benzyl]acrylamide (Mexoryl SW),2-(2H-benzotriazol-2-yl)-4-methyl-δ-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol(Mexoryl SL), 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and amyl4-(dimethylamino)benzoate; esters of cinnamic acid, preferably2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate(octocrylene); esters of salicylic acid, preferably 2-ethylhexylsalicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-methoxy-4′-methylbenzophenone,2,2′-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid,preferably di-2-ethylhexyl 4-methoxybenzmalonate; triazine derivatives,such as e.g.2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and2,4,6-tris[p-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine (Uvinul T150) or bis(2-ethylhexyl)4,4′-[(6-[4-((1,1-dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bisbenzoate(Uvasorb® HEB);2,2-(methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol(Tinosorb M);2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)-1,3,5-triazine(Tinosorb S); propane-1,3-diones, such as e.g.1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione;ketotricyclo(5.2.1.0)decane derivatives, dimethicodiethyl benzalmalonate(Parsol SLX).

A further class of hydrophobic components that can be encapsulated arebiocides. Preferably, the hydrophobic components comprise at least onebiocide capable to dissolve the polyisocyanates (component (A)). Morepreferably, these biocides are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should a biocide notensure adequate solubility of the polyisocyanates, there is the optionof overcoming this disadvantage by using suitable solubility promoters.A biocide is a chemical substance, capable of killing different forms ofliving organisms used in fields, such as medicine, agriculture,forestry, and mosquito control. Usually, biocides are divided into twosub-groups:

-   -   pesticides which includes fungicides, herbicides, insecticides,        algicides, moluscicides, miticides and rodenticides, and    -   antimicrobials which includes germicides, antibiotics,        antibacterials, antivirals, antifungals, antiprotozoals and        antiparasites.

Biocides can also be added to other materials (typically liquids) toprotect the material from biological infestation and growth. Forexample, certain types of quaternary ammonium compounds (quats) can beadded to pool water or industrial water systems to act as an algicide,protecting the water from infestation and growth of algae.

In a preferred form the hydrophobic component comprises a pesticide andoptionally an oil body. In one form suitable pesticides includefungicides, herbicides, insecticides, algicides, moluscicides, miticidesand rodenticides. In another form the term pesticide usually refers toat least one active substance selected from the group of the fungicides,insecticides, nematicides, herbicides, safeners, biopesticides and/orgrowth regulators. Preferred pesticides are fungicides, insecticides,herbicides and growth regulators. Especially preferred pesticides areherbicides. Mixtures of pesticides of two or more of the abovementionedclasses may also be used. The skilled worker is familiar with suchpesticides, which can be found, for example, in the Pesticide Manual,17th Ed. (2015), The British Crop Protection Council, London. Suitableinsecticides are insecticides from the class of the carbamates,organophosphates, organochlorine insecticides, phenylpyrazoles,pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins,juvenile hormone analogs, alkyl halides, organotin compounds nereistoxinanalogs, benzoylureas, diacylhydrazines, METI acarizides, andinsecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin,hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon,chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon,acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitablefungicides are fungicides from the classes of dinitroanilines,allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons,benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones,benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates,carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamideoximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides,dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates,dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides,guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles,imidazolinones, inorganic substances, isobenzofuranones,methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates,oxazolidinediones, oximinoacetates, oximinoacetamides,peptidylpyrimidine nucleosides, phenylacetamides, phenylamides,phenylpyrroles, phenylureas, phosphonates, phosphorothiolates,phthalamic acids, phthalimides, piperazines, piperidines, propionamides,pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines,pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones,quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles,thiazolecarboxamides, thiocarbamates, thiophanates,thiophenecarboxamides, toluamides, triphenyltin compounds, triazines,triazoles. Suitable herbicides are herbicides from the classes of theacetamides, amides, aryloxyphenoxy-propionates, benzamides, benzofuran,benzoic acids, benzothiadiazinones, bipyridylium, carbamates,chloroacetamides, chlorocarboxylic acids, cyclohexanediones,dinitroanilines, dinitrophenol, diphenyl ether, glycines,imidazolinones, isoxazoles, isoxazolidinones, nitriles,N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides,phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles,phenylpyrazolines, phenylpyridazines, phosphinic acids,phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles,pyridazinones, pyridines, pyridinecarboxylic acids,pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates,quinolinecarboxylic acids, semicarbazones,sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones,thiadiazoles, thiocarbamates, triazines, triazinones, triazoles,triazolinones, triazolocarboxamides, triazolopyrimidines, triketones,uracils, ureas.

In another preferred form the hydrophobic component comprises apesticide and an oil body, which may be an water-immiscible organicsolvent. Preferably, the organic solvent has a solubility in water of upto 20 g/l at 20° C., more preferably of up to 5 g/I and in particular ofup to 0.5 g/l. Usually, the organic solvent has a boiling point above100° C., preferably above 150° C., and in particular above 180° C. (at 1bar). Examples for suitable water-immiscible organic solvents aremineral oil fractions of medium to high boiling point, such as keroseneor diesel oil, furthermore oils of vegetable or animal origin, fattyacid glycerides or their methyl or ethyl ester derivatives, commonlycalled methyl- or ethyl oleate, aliphatic, cyclic and aromatichydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes or their derivatives. Mixtures ofwater-immiscible organic solvents may also be used. Preferredwater-immiscible organic solvents are fatty acid glycerides or theirmethyl or ethyl ester derivatives, and/or a hydrocarbons (e.g. aromatichydrocarbons).

A further class of hydrophobic components that can be encapsulated areemollients. Preferably, the hydrophobic components comprise at least oneemollient capable to dissolve the polyisocyanates (component (A)). Morepreferably, these emollients are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should an emollient notensure adequate solubility of the polyisocyanates, there is the optionof overcoming this disadvantage by using suitable solubility promoters.An emollient is a material that softens, soothes, supplies, coats,lubricates, moisturizes, or cleanses the skin. An emollient typicallyaccomplishes several of these objectives such as soothing, moisturizing,and lubricating the skin.

A further class of hydrophobic components that can be encapsulated aredyes. Preferably, the hydrophobic components comprise at least one dyecapable to dissolve the polyisocyanates (component (A)). Morepreferably, these dyes are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should an dye not ensureadequate solubility of the polyisocyanates, there is the option ofovercoming this disadvantage by using suitable solubility promoters.Preferred dyes according to the invention are dyes suitable and approvedfor cosmetic purposes. Examples include cochineal red A (C.I. 16255),patent blue V (C.I. 42051), indigotin (C.I. 73015), chlorophyllin (C.I.75810), quinoline yellow (C.I. 47005), titanium dioxide (C.I. 77891),indanthrene blue RS (C.I. 69800) and madder lake (C.I. 58000). Thesedyes are normally used in concentrations of 0.001 to 0.1% by weight,based on the mixture as a whole.

A further class of hydrophobic components that can be encapsulated arecosmetically active ingredients. Preferably, the hydrophobic componentscomprise at least one cosmetically active ingredient capable to dissolvethe polyisocyanates (component (A). More preferably, these cosmeticallyactive ingredients are capable to dissolve the polyisocyanates withoutextraneous solvents and/or auxiliaries. Should an cosmetically activeingredients not ensure adequate solubility of the polyisocyanates, thereis the option of overcoming this disadvantage by using suitablesolubility promoters. Specifically suitable cosmetically compatible oilbodies are described in Karl-Heinz Schrader, Grundlagen und Rezepturender Kosmetika [Fundamentals and formulations of cosmetics], 2nd edition,Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here.Suitable cosmetically active ingredients are, for example, skin and hairpigmentation agents, tanning agents, bleaches, keratin-hardeningsubstances, antimicrobial active ingredients, photofilter activeingredients, repellent active ingredients, hyperemic substances,keratolytic and keratoplastic substances, antidandruff activeingredients, antiphlogistics, keratinizing substances, activeingredients which have an antioxidative effect and/or free-radicalscavenging effect, skin-moisturizing or -humectant substances, refattingactive ingredients, deodorizing active ingredients, sebostatic activeingredients, plant extracts, antierythimatous or antiallergic activeingredients and mixtures thereof.

A further class of hydrophobic components that can be encapsulated arepharmaceutically ingredients. Preferably, the hydrophobic componentscomprise at least one pharmaceutically ingredient capable to dissolvethe polyisocyanates (compound (A)). More preferably, thesepharmaceutically ingredients are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should apharmaceutically ingredient not ensure adequate solubility of thepolyisocyanates, there is the option of overcoming this disadvantage byusing suitable solubility promoters. In principle, all pharmaceuticalactive substances and prodrugs are suitable for the use of thehydrophobic components according to the invention. These includebenzodiazepines, antihypertensives, vitamins, cytostatics, in particulartaxol, anesthetics, neuroleptics, antidepressants, antibiotics,antimycotics, fungicides, chemotherapeutics, urologics, thrombocyteaggregation inhibitors, sulfonamides, spasmolytics, hormones,immunoglobulins, sera, thyroid therapeutic agents, psychopharmacologicalagents, antiparkinsonians and other antihyperkinetic agents,ophthalmics, neuropathy preparations, calcium metabolism regulators,muscle relaxants, narcotics, antilipemics, hepatic therapeutic agents,coronary agents, cardiacs, immunotherapeutics, regulatory peptides andtheir inhibitors, hypnotics, sedatives, gynecological agents, antigouts,fibrinolytic agents, enzyme preparations and transport proteins, enzymeinhibitors, emetics, circulation-promoting agents, diuretics,diagnostics, corticoids, cholinergics, bile duct therapeutics,antiasthmatics, broncholytics, beta-receptor blockers, calciumantagonists, ACE inhibitors, antiarteriosclerotics, antiinflammatories,anticoagulants, antihypotensives, antihypoglycemics, antihypertonics,antifibrinolytics, antiepileptics, antiemetics, antidotes,antidiabetics, antiarrhythmics, antianemics, antiallergics,anthelmintics, analgesics, analeptics, aldosterone antagonists andslimming agents. Examples of suitable pharmaceutical active substancesare in particular the active substances mentioned in paragraphs 0105 to0131 of US 2003/0157170.

The hydrophopbic component preferably comprises a pharmaceuticallyacceptable auxiliary. Of pharmaceutical acceptability are theauxiliaries that are known for use in the field of pharmacy, foodtechnology and related fields, in particular the auxiliaries listed inrelevant pharmacopoeia (e.g. DAB, Ph. Eur., BP, NF), as well as otherauxiliaries whose properties do not preclude a physiological use.Suitable cosmetically and pharmaceutically acceptable auxiliaries arealso described in Fiedler, H. P. Lexikon der Hilfsstoffe for Pharmazie,Kosmetik und angrenzende Gebiete [Lexicon of the auxiliaries forpharmacy, cosmetics and related fields], 4th edition, Aulendorf:ECV-Editio-Kantor-Verlag, 1996.

A further class of hydrophobic components that can be encapsulated arecompositions used for industrial or institutional or hospitalapplications. Preferably, the hydrophobic components comprise at leastone composition used for industrial or institutional or hospitalapplications capable to dissolve the polyisocyanates (component (A)).More preferably, these are compositions used for industrial orinstitutional or hospital applications are capable to dissolve thepolyisocyanates without extraneous solvents and/or auxiliaries. Should acomposition used for industrial or institutional or hospitalapplications not ensure adequate solubility of the polyisocyanates,there is the option of overcoming this disadvantage by using suitablesolubility promoters. Suitable compositions used for industrial orinstitutional or hospital applications are, for example, chelants ofheavy metal and hardness ions (builders), scale inhibiting agents,corrosion inhibiting agents, deflocculating/dispensing agents, stainremoval agents, bleach stabilizing agents, protecting agents ofperoxygen labile ingredients, photobleaching enhancing agents,thickener/viscosity modifying agents, crystal growth modificationagents, sludge modification agents, surface modification agents,processing aids, electrolyte, hydrolytic stability agents, alkalinityagents and the like. The lipophilic components are compounds which arealso useful for certain industrial applications, such as acid cleaners,aluminum etching, boiler cleaning, water treatment, bottle washing,cement modification, dairy cleaners, desalination, electrochemicalmachining, electroplating, metal finishing, paper mill evaporations, oilfield water treatment, paper pulp bleaching, pigment dispersion, tracemetal carrier for fertilizers, irrigation, circuit cleaning and thelike.

A further class of hydrophobic components that can be encapsulated aretextile treatment compositions. Preferably, the hydrophobic componentscomprise at least one textile treatment composition capable to dissolvethe polyisocyanates (component (A)). More preferably, these textiletreatment compositions are capable to dissolve the polyisocyanateswithout extraneous solvents and/or auxiliaries. Should a textiletreatment composition not ensure adequate solubility of thepolyisocyanates, there is the option of overcoming this disadvantage byusing suitable solubility promoters. Suitable textile treatmentcompositions are softening compositions, such as liquid fabricsofteners, fabric softening rinses, fabric softening sheets, tissuepapers, paper towels, facial tissues, sanitary tissues, toilet paper andthe like.

A further class of hydrophobic components that can be encapsulated arevitamins. Suitable water-insoluble vitamins and provitamins are e.g.vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherolderivatives, such as tocopherol acetate and vitamin K.

A further class of hydrophobic components that can be encapsulated areanti-oxidants. Suitable anti-oxidants includes, for example: alkylatedmonophenols, alkylthiomethylphenols, hydroquinones and alkylatedhydroquinones, tocopherols, hydroxylated thiodiphenyl ether,alkylidenebisphenols, benzyl compounds, hydroxybenzylated malonates,hydroxybenzyl aromatics, triazine compounds, benzylphosphonates,acylaminophenols, esters ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric orpolyhydric alcohols, esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydricor polyhydric alcohols, esters ofβ-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric orpolyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylaceticacid with monohydric or polyhydric alcohols, amides ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ascorbic acid(vitamin C) or aminic antioxidants.

A further class of hydrophobic components that can be encapsulated areperfumes and fragrances. Suitable fragrances employed according thepresent invention are conventional ones known in the art. Suitableperfume compounds and compositions can be found in the art includingU.S. Pat. No. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; U.S.Pat. No. 4,209,417, Whyte, issued Jun. 24, 1980; U.S. Pat. No.4,515,705, Moeddel, issued May 7, 1985; U.S. Pat. No. 4,152,272, Young,issued May 1, 1979; U.S. Pat. No. 5,378,468 Suffis et al.; U.S. Pat. No.5,081,000 Akimoto et al., issued Jan. 14, 1992; U.S. Pat. No. 4,994,266Wells, issued Feb. 19, 1991; U.S. Pat. No. 4,524,018 Yemoto et al.,issued Jun. 18, 1985; U.S. Pat. No. 3,849,326 Jaggers et al., issuedNov. 19, 1974; U.S. Pat. No. 3,779,932 Jaggers et al., issued Dec. 18,1973; JP 07-179,328 published Jul. 18, 1995; JP 05-230496 published Sep.7, 1993; WO 96/38528 published Dec. 5, 1996; WO 96/14827 published May23, 1996; WO 95/04809 published Feb. 16, 1995; and WO 95/16660 publishedJun. 22, 1995; all of said U.S. patents and U.S. references beingincorporated herein by reference. In addition, P. M. Muller, D.Lamparsky Perfumes Art, Science, & Technology Blackie Academic &Professional, (New York, 1994) is included herein by reference.Fragrances can be classified according to their volatility. The highlyvolatile, low boiling, perfume ingredients typically have boiling pointsof about 250° C. or lower. The moderately volatile perfume ingredientsare those having boiling of from about 250° C. to about 300° C. The lessvolatile, high boiling, perfume ingredients are those having boilingpoints of about 300° C. or higher. Many of the perfume ingredients asdiscussed hereinafter along with their odor and/or flavor characters,and their physical and chemical properties, such as boiling point andmolecular weight, are given in “Perfume and Flavor Chemicals (AromaChemicals),” Steffen Arctander, published by the author, 1969,incorporated herein by reference.

The present invention relates also to a process for the preparation ofmicrocapsules or a dispersion of the microcapsules as defined above.

Embodiment (2): the process for the preparation of a microcapsuledispersion, wherein the microcapsules are defined above and the coreessentially contains only a hydrophobic component comprising thefollowing steps:

-   a) providing a premix (Ib) comprising the hydrophobic component(s)    to be encapsulated (Cb), optionally a hydrophobic medium that is    liquid at 20° C. and 1023 mbar different from (Cb), and at least one    component (A) as defined above, and-   b) mixing the premix (Ib) provided in step a) with a hydrophilic    medium comprising at least one hydrophilic protective colloid, at    least one component (B1) as defined above, and reacting the    resulting mixture to form microcapsules dispersed in the hydrophilic    medium.

In a preferred embodiment (2a) the process comprising the steps:

-   a) providing a premix (IIIb) comprising at least one protective    colloid in an aqueous solution,-   b) providing a premix (IIb) comprising at least one component A),    which is defined above and at least one hydrophobic component, and    optionally the hydrophobic medium,-   c) mixing premix (IIIb) and premix (IIb) until an dispersion (III)    is formed,-   d) adding an aqueous solution (IV) containing at least one component    B1), which is defined above, to the emulsion formed in step c),-   e) forming a dispersion of microcapsules by heating the mixture    obtained in step d) to a temperature of at least 30° C. until    microcapsules are formed.

Preferrably the hydrophobic component (Cb) is soluble in the hydrophobicmedium.

Hydrophilic medium is to be understood as meaning either water or thoseaqueous solutions which, apart from water, comprise up to 20% by weightof a water-miscible organic solvent, such as C₁- to C₄-alkanols, inparticular methanol, ethanol, isopropanol or a cyclic ether, such astetrahydrofuran.

Suitable hydrophilic media are also ethylene glycol, glycerol,polyethylene glycols and butylene glycol, and their mixtures. Preferredhydrophilic media are water and mixtures of these solvents with water.

Typically hydrophobic medium comprises (preferably consists of) the oilbody.

A “stable dispersion” in the sense of the present invention denotes adispersion of microcapsules which, upon visible inspection, shows nosign of phase separation, such as creaming, settling, precipitation orcoagulation when stored for a period of two weeks at a temperature of50° C.

The term “aqueous solution” in the sense of the invention denotes waterand mixtures of water with at least one at least partly water-miscibleorganic solvent. Suitable organic solvents are e.g. C₁-C₄-alkanols. TheC₁-C₄-alkanols are preferably selected from among methanol, ethanol,n-propanol, isopropanol and n-butanol. Mixtures of at least oneC₁-C₄-alkanol with water preferably comprise from 0.1 to 99.9% byweight, particularly preferably from 0.2 to 50% by weight, in particularfrom 0.3 to 10% by weight of at least one C₁-C₄-alkanol, based on thetotal weight of the mixture. In a special embodiment the aqueoussolution consists of water.

In one preferred embodiment, the process is carried out as follows:

-   a) providing a premix (IIIb) comprising at least one protective    colloid in an aqueous solution and adjusting the pH in a range of    from 5 to 12,-   b) providing a further premix (IIb) comprising at least one    hydrophobic component and component A),-   c) mixing premix (IIIb) and premix (IIb) until an dispersion is    formed and adjusting the pH of the resulting dispersion in a range    of from 5 to 10,-   d) adding an aqueous solution (IV) containing at least one    polyfunctional amine B1) to the dispersion formed in step c),-   e) forming a dispersion of microcapsules by heating the mixture    obtained in step d) to a temperature of at least 30° C. until    microcapsules are formed.

Step a)

Premix (IIIb) provided in step a) contains an aqueous solvent. Suitablesolvents are water and mixtures of water with at least onewater-miscible organic solvent. Suitable water-miscible organic solventare mentioned above. Preferably, the solvent is essentially water.

The aqueous solution provided in step a) of embodiment (2a), such as inpremix (IIIb), or in step b) of embodiment (2), usually comprises atleast one protective colloid, such as an hydrophilic protective colloid.

During the reaction between the component (A) and component (B), aprotective colloid, preferably a hydrophilic protective colloid, may bepresent. Protective colloids are usually polymer systems which, insuspensions or dispersions, prevent a clumping together (agglomeration,coagulation, flocculation) of the emulsified, suspended or dispersedcomponents. During solvation, protective colloids bind large amounts ofwater and in aqueous solutions produce high viscosities depending on theconcentration. Within the context of the process described herein, theprotective colloid may also have emulsifying properties. The aqueousprotective colloid solution is likewise preferably prepared withstirring.

Preferably, the protective colloid (e.g. the hydrophilic protectivecolloid) is selected from polyvinylpyrrolidones, polyvinyl alcohols,maleic-vinyl copolymers, sodium lignosulfonates, maleicanhydride/styrene copolymers, ethylene/maleic anhydride copolymers,copolymers of ethylene oxide, propylene oxide and ethylenediamine, fattyacid esters of polyethoxylated sorbitol, sodium dodecylsulfate andmixtures thereof. More preferably, the protective colloid is selectedfrom polyvinylpyrrolidones, polyvinyl alcohols and mixtures thereof.Polyvinylpyrrolidones are particularly preferred.

The polyvinylpyrrolidones preferably have a K value (determined at 25°C. in a 1% by weight aqueous or ethanolic solution) of at least 10,particularly preferably of at least 20, more preferably of at least 80.Determination of the K value is described in H. Fikentscher “Systematikder Cellulosen auf Grund ihrer Viskosität in Lsung”, Cellulose-Chemie 13(1932), 58-64 and 71-74, and Encyclopedia of Chemical Technology, Vol.21, 2^(nd) edition, 427-428 (1970).

Suitable commercially available polyvinylpyrrolidones are the Kollidontrademarks from BASF SE. Preferred polyvinylpyrrolidones useful in thepractice of the present invention are available in three grades:Kollidon® 25 (BASF Corporation), Kollidon® 90 (BASF Corporation), andKollidon® CI-M (BASF Corporation). Kollidon® 25 has a weight averagemolecular weight of 28000-34000. Kollidon® 90 has a molecular weightaverage of 1000000-1500000. Further commercially availablepolyvinylpyrrolidones are Kollidon 12 which has a weight averagemolecular weight of 2000-3000, Kollidon 17 which has a weight averagemolecular weight of 7000-11000 and Kollidon 30 which has a weightaverage molecular weight of 44000-54000.

Particular protective colloids include polyvinyl alcohol copolymershaving a degree of hydrolysis in the range of 85 to 99.9%. As usedherein, the term “polyvinyl alcohol copolymer” means a polymer of vinylalcohol/vinyl acetate with comonomers. It is known that polyvinylalcohol is produced by hydrolysis (deacetylation) of polyvinylacetate,whereby ester groups of polyvinyl acetate are hydrolysed into hydroxylgroups, thus forming polyvinyl alcohol. The degree of hydrolysisreflects the percentage of groups that are converted by hydrolysis. Theterm “polyvinyl alcohol”, qualified by a degree of hydrolysis, meanstherefore, a vinyl polymer containing both ester and hydroxyl groups. Ina particular embodiment of the invention, copolymers of polyvinylalcohol with a degree of hydrolysis in the range of 85 to 99.9%, moreparticularly 85 to 95% may be used as protective colloids. The degree ofhydrolysis can be determined by techniques well known in the art, forexample, according to DIN 53401.

The polyvinyl alcohol copolymers contain addition comonomers, that is,comonomers that are polymerized with a vinyl ester in a first step,followed by hydrolysis of the ester groups to form the copolymer ofpolyvinyl alcohol in a second step. Copolymers may be formed by radicalpolymerization of vinyl acetate and comonomers in a manner known per se.Polyvinyl alcohol copolymers may contain unsaturated hydrocarbons ascomonomers. These hydrocarbons may be modified with charged ornon-charged functional groups. Particular comonomers include, but arenot limited to: unsaturated hydrocarbons with 2 or 3 carbon atoms and nofunctional groups, thylene; unsaturated hydrocarbons having 2 to 6carbon atoms and non-charged functional groups, such as hydroxyl groups,e.g. buten-1,4-diol; unsaturated hydrocarbons having anionic groups,such as carboxyl, and/or sulphonic acid groups; unsaturated hydrocarbonshaving cationic groups, such as quaternary ammonium groups.

Particular copolymers of polyvinyl alcohol include those having a degreeof hydrolysis of 85 to 99.9%, and more particularly 85 to 95%; and whichcontain: 0.1 to 30 mol % of comonomers containing anionic groups asmentioned above; or 0.1 to 30 mol % of comonomers containing cationicgroups as mentioned above; or 0.1 to 30 mol % of comonomers withunsaturated hydrocarbons having 2 to 6 carbon atoms and non-chargedfunctional groups, especially two hydroxyl groups, wherein mol % isbased on the vinyl acetate/comonomer polymerization mixture.

Suitable copolymers of polyvinyl alcohol and comonomers having 1,2 diolstructures are described in EP 2 426 172 and EP 2 648 211 which areherein incorporated by reference. Particularly preferred polyvinylalcohols are the Mowiol types available from Kuraray

The protective colloid can be, but does not have to be, a constituent ofthe capsule shell. The protective colloid may be, but does not have tobe, a constituent of the capsule shell with amounts from 0.1 to at most15% by weight, but preferably in the range from 1 to 5% by weight and inparticular from 1.5 to 3% by weight, based on the weight of thecapsules, being possible here.

Combinations of two or more different protective colloids may also beemployed in the present invention. In a further preferred embodiment,the protective colloid comprises or consists of at least onepolyvinylpyrrolidone.

Premix (Ib) or premix (IIb) or premix (IIIb) may also contain at leastone emulsifier. Emulsifiers include non-ionic, cationic, anionic andzwitterionic surfactants. Suitable non-ionic surfactants are selectedfrom the group consisting of products of the addition of 2 to 30 molethylene oxide and/or 0 to 5 mol propylene oxide onto linear C₆₋₂₂ fattyalcohols, onto C₁₂₋₂₂ fatty acids, onto alkyl phenols containing 8 to 15carbon atoms in the alkyl group and onto alkylamines containing 8 to 22carbon atoms in the alkyl group; alkyl oligoglycosides containing 8 to22 carbon atoms in the alkyl group and ethoxylated analogs thereof;addition products of 1 to 15 mol ethylene oxide onto castor oil and/orhydrogenated castor oil; addition products of 15 to 60 mol ethyleneoxide onto castor oil and/or hydrogenated castor oil; partial esters ofglycerol and/or sorbitan with unsaturated, linear or saturated branchedfatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylicacids containing 3 to 18 carbon atoms and addition products thereof onto1 to 30 mol ethylene oxide; partial esters of polyglycerol (averagedegree of self-condensation 2 to 8), polyethylene glycol (molecularweight 400 to 5,000), trimethylolpropane, pentaerythritol, sugaralcohols (for example sorbitol), alkyl glucosides (for example methylglucoside, butyl glucoside, lauryl glucoside) and polyglucosides (forexample cellulose) with saturated and/or unsaturated, linear or branchedfatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylicacids containing 3 to 18 carbon atoms and addition products thereof onto1 to 30 mol ethylene oxide; mixed esters of pentaerythritol, fattyacids, citric acid and fatty alcohol and/or mixed esters of fatty acidscontaining 6 to 22 carbon atoms, methyl glucose and polyols, preferablyglycerol or polyglycerol, mono-, di- and trialkyl phosphates and mono-,di- and/or tri-PEG-alkyl phosphates and salts thereof, wool waxalcohols, polysiloxane/polyalkyl/polyether copolymers and correspondingderivatives, block copolymers, for example Polyethyleneglycol-30Dipolyhydroxystearate; polymer emulsifiers, for example Pemulen types(TR-1, TR-2) of Goodrich; polyalkylene glycols and glycerol carbonateand ethylene oxide addition products.

Step b

Premix (IIb) provided in step b) comprises at least one component (A)and at least one lipophilic component.

Premix (IIb) is generally in liquid form. Preferably, premix (IIb)contains no or only a minor amount of solid components. In the sense ofthe invention a minor amount means that the amount of solid componentsis at the most 5% by weight, preferably at the most 1% by weight, morepreferably at the most 0.1% by weight, based on the total weight ofpremix (IIb). In particular, premix (IIb) contains no solid components.

Premix (IIb) optionally contains at least one organic solvent. Anorganic solvent is particularly used if the mixture of the employedcomponent (A) and the employed lipophilic components is not liquid underthe conditions of process step b).

In a further preferred embodiment of the present invention, thehydrophobic component is used as the solvent for premix (IIb).Preferably, premix (IIb) contains no extraneous solvents apart from thehydrophobic component.

Step c)

In step c) the premix (IIIb) and premix (IIb) are mixed until andispersion (III) is formed. In order to form an dispersion (III) in thepresent process, the premix (IIIb) and premix (IIb) are emulsified byprocesses known to the person skilled in the art, e.g. by introducingenergy into the mixture through stirring using a suitable stirrer untilthe mixture emulsifies.

A preferred embodiment is a process, wherein

-   -   a target range for the volume average diameter of the droplets        of the hydrophobic (discontinuous phase) of the resulting        dispersion (III) is predefined,    -   the actual volume average diameter of the droplets of the        hydrophobic phase in the mixture of premix (IIIb) and premix        (IIb) is determined,    -   the speed of the stirrer and/or the time of stirring of the        mixture are adjusted until the target value volume average        diameter of the droplets of the hydrophobic phase of the        resulting dispersion (III) is reached in order to obtain the        predefined target volume average diameter of the droplets of the        hydrophobic phase.

Suitable devices for controlling the volume average diameter of thedroplets of discontinuous phase of the resulting dispersion are known tothose skilled in the art. Such devises are based, for example, on lightscattering measurements. Suitable light scattering measurements areknown to those skilled in the art and are commercially available from,for example, Malvern Instruments, e.g. Malvern autosizer.

The rate of stirring of the mixture of premix (IIIb) and premix (IIb) instep c) is adjusted to influence the size of droplets of hydrophobicphase in the aqueous phase. After a period of vigorous stirring, anemulsion is obtained, in which the premix (IIb) is dispersed as tinydroplets in the aqueous solution of premix (IIIb). The mixture of premix(IIIb) and premix (IIb) is stirred vigorously. Preferred stirrer are MIGstirrer, propellers stirrer, paraviscs stirrer, INTERMIG stirrer andisojet stirrer. The pH is preferably adjusted using aqueous bases,preference being given to using sodium hydroxide solution (e.g. 5%strength by weight). Preferably the pH of emulsion (III) is adjustedfrom 3 to 12, in particular between 4 to 10, and more particular in therange from 5 to 10.

Step d)

The aqueous solution (IV) comprises at least one component (B).Preferably, the aqueous solution (IV) comprises at least onepolyfunctional amine. Suitable amines are mentioned below. In apreferred embodiment, the aqueous solution comprises a polylysine.

Step e)

The polyaddition reaction in step e) is generally performed at atemperature of at least 30° C., preferably 50° C., more preferably in arange of from 65° C. to 90° C. and in particular 75° C. to 90° C., inorder to ensure sufficiently rapid reaction progress. Here, it may bepreferred to increase the temperature in stages (e.g. in each case by10° C.) until then, following completion of the reaction, the dispersionis cooled down to room temperature (21° C.).

The reaction time typically depends on the reaction amount andtemperature used. The period of time for the polyaddition reaction isranging from a few minutes to several hours. Usually, microcapsuleformation is established between ca. 60 minutes to 6 h or up to 8 h atthe temperatures defined above.

A further aspect of the invention relates to the processes according tothe invention, wherein the obtained microcapsule dispersion described inembodiment (1), embodiment (2) or embodiment (2a), as described above,may be dryed to provide microcapsules in solid form, preferably in formof a powder.

In another embodiment, the process according to the invention comprisingan additional drying step) subjecting the microcapsules or microcapsuledispersion obtained by the process described above in embodiments (1),(2) and (2a) to a drying. The microcapsules or the microcapsuledispersion may be dried using techniques known in the art. For example,the solid capsules can be isolated by filtration and dryed. Drying ofthe isolated capsules may be performed by heating, e.g. in an oven or bycontact with a heated gas stream. Preferably, drying of the dispersionis carried out by spray drying or fluid-bed drying.

Spray drying techniques and apparatus are well known in the art. Aspray-drying process pushes suspended capsules through a nozzle and intoa drying chamber. The capsules may be entrained in a fluid (such as air)that moves inside of a drying chamber. The fluid (which may be heated,for example at a temperature of 150 and 120° C., more preferably between170° C. and 200° C., and still more preferably between 175° C. and 185°C.) causes the liquid to evaporate, leaving behind the dried capsuleswhich can then be collected from the process equipment and furtherprocessed. It is conventional to mix spray dried capsules with flow aidsto produce a flowable powder that are not susceptible to caking. Flowaids include silicas or silicates, such as precipitated, fumed orcolloidal silicas; starches; calcium carbonate; sodium sulphate;modified cellulose; zeolites; or other inorganic particulates known inthe art. It is quite common, given the high temperatures and impactionforces encountered during a spray drying procedure, for core shellcapsules to lose some of their core material. Furthermore, it may not bepossible to work at sufficiently high temperatures for a sufficientlylong period of time to drive off all moisture from the dispersion,without compromising the thermal stability of the capsules. Accordingly,the capsules emerging from a spray-drying process, as herein described,may contain small amounts of surface oil as well as residual moisture.

If the microcapsules or microcapsule dispersion of the presentinvention, irrespectively of its core material, are intended to bestored in the form of a dispersion, the pH of the dispersion is adjustedto a level of about 5 to 10. This may be achieved with the addition toan alkaline dispersion of a suitable acid, such as citric acid or formicacid.

In a further embodiment, the microcapsule or microcapsules or dispersionof the microcapsules, irrespectively of its core material, may containnon-encapsulated, i.e. free hydrophobic components, external of thecapsules in the aqueous dispersion.

It is likewise possible for the ingredients of the core to migrate fromthe core of the microcapsules (i.e. the hydrophobic component and/orfurther materials present in the core) into the shell.

In a further embodiment of the invention, the microcapsule ormicrocapsules or dispersion of the microcapsules irrespectively of itscore material, comprises at least one preservative in order to preventmicrobial contamination of the microcapsules. The preservative may becontained in the aqueous suspending medium of the dispersion. Suitablepreservatives include quaternary compounds, biguanide compounds,ethylhexylglycerin, caprylyl glycol, phenezhyl alcohol, propandiol,undecyl alcohol, tocopherol and mixtures thereof. Non-limiting examplesof quaternary compounds include benzalkonium chlorides and/orsubstituted benzalkonium chlorides, di(C₆-C₁₄)alkyl di short chain(C₀₁₋₄ alkyl and/or hydroxyalkl) quaternary, N-(3-chloroallyl)hexaminium chlorides, benzethonium chloride, methylbenzethoniumchloride, cetylpyridinium chloride, diester quaternary ammoniumcompounds and mixtures thereof. Preferred commercially availablebenzalkonium chlorides are sold by Lonza under the trademark Barquat®,Maquat® trademarks from Mason, Variquat® trademarks from Witco/Sherexand Hyamine® trademarks from Lonza. Preferred commercially availabledi(C₆-C₁₄)alkyl di short chain (C₁₋₄ alkyl and/or hydroxyalkl)quaternary are sold by Lonza under the trademark Bardac®. Preferredcommercially available N-(3-chloroallyl) hexaminium chlorides are soldby Dow under the trademark Dowicide® and Dowicil®. Preferredcommercially available benzethonium chlorides are sold by Rohm & Haasunder the trademark Hyamine®. Preferred commercially availablemethylbenzethonium chlorides are sold by Rohm & Haas under the trademarkHyamine® 10*. Preferred commercially available cetylpyridinium chloridesare sold by Merrell Labs under the trademark Cepacol chloride. Examplesof preferred dialkyl quaternary compounds are di(C₈-C₁₂)dialkyl dimethylammonium chlorides. Preferred commercially available dialkyl quaternaryand dioctyldimethylammonium chlorides are sold by Lonza under thetrademark Bardac® 22 and (Bardac® 2050). The quaternary compounds usefulas cationic preservatives and/or antimicrobial agents herein arepreferably selected from the group consisting of dialkyldimethylammoniumchlorides, alkyldimethylbenzylammonium chlorides,dialkylmethylbenzylammonium chlorides, and mixtures thereof. Otherpreferred cationic antimicrobial actives useful herein includediisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride and(methyl)diisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride(i.e. methylbenzethonium chloride). Preferred commercially availablequaternary compounds are sold by Rohm & Haas under the trademarkHyamine® 1622. Preferred commercially available preservatives are soldby Schulke under the trademark Sensiva PA20, Sensiva PA40, Sensiva SC10,Sensiva SC50.

The microcapsule composition, microapsules and dispersion ofmicrocapsules as defined above can be used in a large number ofdifferent applications, depending on the type of lipophilic component.

A preferred embodiment of the invention is the use of the microcapsuleor of microcapsules dispersion irrespectively of its core, materialaccording to the invention for a personal care composition or acomposition used for industrial or institutional or hospitaldisinfection, a material protection composition or a pharmaceuticalcomposition or a plant protection composition or home care products.

A preferred embodiment of the invention is the use of the microcapsulesor of microcapsules dispersion irrespectively of its core materialaccording to the invention for a cosmetic composition, a hygienecomposition, a composition for industrial or institutional or hospitalcleaning or disinfection, laundry detergents, fabric softeners,dishwashing liquids, household cleaners or industrial cleaners, oilrecovery, adhesives, coatings, or constructions agro formulations.

Preference is given to using the microcapsules for the finishing of allkind of nonwovens, like wipes (for example wet wipes or dry wipes forcosmetic or cleaning purposes), but also for finishing papers (includingwallpapers, toilet paper or papers for books and newsletters), forfinishing diapers or sanitary napkins and similar hygienic products ortextiles, e.g. in order to finish the papers or textiles with a dye oran insecticide, or in cosmetic compositions, e.g. for producingsunscreen compositions which comprise the UV filter in the form of themicrocapsules. Another use pertains to finishing diapers or sanitarynapkins and similar hygienic products. Furthermore the microcapsules maybe used in massage oils or cremes or personal lubricants, andsuppositories, e.g. to provide this products with antiinflammatoryactives.

A preferred embodiment of the invention is the use of the microcapsulesor of microcapsules dispersion according to the invention in finishingof textiles, papers or nonwovens.

A further aspect of the present invention is the use of a microcapsuledispersion as described above or obtained by the above-described processin a pharmaceutical composition. Suitable pharmaceutical activesubstances and prodrugs include benzodiazepines, antihypertensives,vitamins, cytostatics, in particular taxol, anesthetics, neuroleptics,antidepressants, antibiotics, antimycotics, fungicides,chemotherapeutics, urologics, thrombocyte aggregation inhibitors,sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroidtherapeutic agents, psychopharmacological agents, antiparkinsonians andother antihyperkinetic agents, ophthalmics, neuropathy preparations,calcium metabolism regulators, muscle relaxants, narcotics,antilipemics, hepatic therapeutic agents, coronary agents, cardiacs,immunotherapeutics, regulatory peptides and their inhibitors, hypnotics,sedatives, gynecological agents, antigouts, fibrinolytic agents, enzymepreparations and transport proteins, enzyme inhibitors, emetics,circulation-promoting agents, diuretics, diagnostics, corticoids,cholinergics, bile duct therapeutics, antiasthmatics, broncholytics,beta-receptor blockers, calcium antagonists, ACE inhibitors,antiarteriosclerotics, antiinflammatories, anticoagulants,antihypotensives, antihypoglycemics, antihypertonics, antifibrinolytics,antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics,antianemics, antiallergics, anthelmintics, analgesics, analeptics,aldosterone antagonists and slimming agents. Examples of suitablepharmaceutical active substances are in particular the active substancesmentioned in paragraphs 0105 to 0131 of US 2003/0157170.

The formulation base of pharmaceutical compositions preferably comprisesat least one pharmaceutically acceptable auxiliary. Pharmaceuticallyacceptable auxiliaries are auxiliaries which are known for use in thefield of pharmaceuticals, food technology and related fields, inparticular those listed in the relevant pharmacopeias (e.g., DAB, Ph.Eur., BP, NF), and other auxiliaries, the properties of which do notpreclude a physiological application.

A further aspect of the present invention is the use of a microcapsuledispersion as described above or obtained by the above-described processin a cosmetic composition. Suitable cosmetically active substances andcosmetic auxiliaries are described in Karl-Heinz Schrader, Grundlagenund Rezepturen der Kosmetika [Fundamentals and formulations ofcosmetics], 2nd edition, Verlag HOthig, Heidelberg, which is herebyincorporated by reference.

Suitable cosmetic auxiliaries are described, for example, in Fiedler, H.P., Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzendeGebiete [Encyclopedia of Auxiliaries for Pharmaceuticals, Cosmetics andRelated Fields], 4th edition, Aulendorf: ECV-Editio-Kantor-Verlag, 1996.Suitable cosmetic auxiliaries can be lubricants, wetting agents,emulsifying and suspending agents, preservatives, antioxidants,antiirritatives, chelating agents, emulsion stabilizers, film-formingagents, gel formers, odor-masking agents, resins, hydrocolloids,solvents, solubility promoters, neutralizing agents, permeationaccelerators, pigments, quaternary ammonium compounds, refatting andsuperfatting agents, ointment, cream or oil base substances, siliconederivatives, stabilizers, sterilants, propellants, drying agents,opacifiers, thickeners, waxes, softeners or white oils.

A further aspect of the present invention is the use of a microcapsuledispersion as described above or obtained by the above-described processin a hygiene composition. A further aspect of the present invention isthe use of a microcapsule dispersion as described above or obtained bythe above-described process in a composition for industrial orinstitutional or hospital cleaning disinfection. A further aspect of thepresent invention is the use of a microcapsule dispersion as describedabove or obtained by the above-described process in a laundrydetergents. A further aspect of the present invention is the use of amicrocapsule dispersion as described above or obtained by theabove-described process in a fabric softners. A further aspect of thepresent invention is the use of a microcapsule dispersion as describedabove or obtained by the above-described process in a dishwashingliquids. A further aspect of the present invention is the use of amicrocapsule dispersion as described above or obtained by theabove-described process in a household cleaners. A further aspect of thepresent invention is the use of a microcapsule dispersion as describedabove or obtained by the above-described process in a industrialcleaners. A further aspect of the present invention is the use of amicrocapsule dispersion as described above or obtained by theabove-described process in oil recovery. A further aspect of the presentinvention is the use of a microcapsule dispersion as described above orobtained by the above-described process in a adhesive. A further aspectof the present invention is the use of a microcapsule dispersion asdescribed above or obtained by the above-described process in coatings.A further aspect of the present invention is the use of a microcapsuledispersion as described above or obtained by the above-described processin or as construction additives composition. Suitable constructionadditives are selected from plasticizers, superplasticizers, shrinkagereducing agents, corrosion inhibitors, defoaming agents, retardants,accelerators, seeding agents, concrete levelling agents,hydrophobization agents, accelerators for cementitious systems andmixtures thereof. Suitable hydrophobization and shrinkage reducingagents are silicon oil, reactive siloxanes, calcium soaps e.g. calciumstearate; hemiterpene alcohol e.g. isoprenol and fluore-basedorgano-compounds.

A further aspect of the present invention is the use of a microcapsuledispersion as described above or obtained by the above-described processin agro formulations. When used in agro formulations the hydrophobiccomponent usually comprises a pesticide.

The microcapsules comprising a hydrophobic component selected frompesticides may optionally comprise auxiliaries which are customary inagrochemical formulations. The auxiliaries used depend on the particularapplication form and active substance, respectively. Examples forsuitable auxiliaries are dispersants or emulsifiers (such as furthersolubilizers, protective colloids, surfactants and adhesion agents),organic and anorganic thickeners, bactericides, anti-freezing agents,anti-foaming agents, if appropriate colorants and tackifiers or binders(e. g. for seed treatment formulations). Examples for suitableauxiliaries are solvents, liquid carriers, solid carriers or fillers,surfactants, further dispersants, emulsifiers, wetters, furtheradjuvants, solubilizers, penetration enhancers, protective colloids,adhesion agents, thickeners, humectants, repellents, attractants,feeding stimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders. Suitablesurfactants are surface-active compounds, such as anionic, cationic,nonionic and amphoteric surfactants, block polymers, polyelectrolytes,and mixtures thereof. Such surfactants can be used as emusifier,dispersant, solubilizer, wetter, penetration enhancer, protectivecolloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

The present invention furthermore relates to a method of controllingphytopathogenic fungi and/or undesired plant growth and/or undesiredinsect or mite attack and/or for regulating the growth of plants,wherein the microcapsules or the microcapsule dispersion, where thehydrophobic component comprises a pesticide, are allowed to act on therespective pests, their environment or the crop plants to be protectedfrom the respective pest, on the soil and/or on undesired plants and/oron the crop plants and/or on their environment.

Examples of suitable crop plants are cereals, for example wheat, rye,barley, triticale, oats or rice; beet, for example sugar or fodder beet;pome fruit, stone fruit and soft fruit, for example apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries, currantsor gooseberries; legumes, for example beans, lentils, peas, lucerne orsoybeans; oil crops, for example oilseed rape, mustard, olives,sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans;cucurbits, for example pumpkins/squash, cucumbers or melons; fibercrops, for example cotton, flax, hemp or jute; citrus fruit, for exampleoranges, lemons, grapefruit or tangerines; vegetable plants, for examplespinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes,potatoes, pumpkin/squash or capsicums; plants of the laurel family, forexample avocados, cinnamon or camphor; energy crops and industrialfeedstock crops, for example maize, soybeans, wheat, oilseed rape, sugarcane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine(dessert grapes and grapes for vinification); hops; grass, for exampleturf; sweetleaf (Stevia rebaudania); rubber plants and forest plants,for example flowers, shrubs, deciduous trees and coniferous trees, andpropagation material, for example seeds, and harvested produce of theseplants.

The term crop plants also includes those plants which have been modifiedby breeding, mutagenesis or recombinant methods, including thebiotechnological agricultural products which are on the market or in theprocess of being developed. Genetically modified plants are plants whosegenetic material has been modified in a manner which does not occurunder natural conditions by hybridizing, mutations or naturalrecombination (i.e. recombination of the genetic material). Here, one ormore genes will, as a rule, be integrated into the genetic material ofthe plant in order to improve the plant's properties. Such recombinantmodifications also comprise posttranslational modifications of proteins,oligo- or polypeptides, for example by means of glycosylation or bindingpolymers such as, for example, prenylated, acetylated or farnesylatedresidues or PEG residues.

The user applies the microcapsule or the microcapsule dispersion usuallyfrom a predosage device, a knapsack sprayer, a spray tank, a sprayplane, or an irrigation system. Usually, the agrochemical composition ismade up with water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, very preferably50 to 200 liters of the ready-to-use spray liquor are applied perhectare of agricultural useful area.

EXAMPLES

The following examples are intended to further illustrate the presentinvention without limiting its scope in any way.

Determination of the Isocyanate Content was made as follows: Sampleswere taken from the reaction mixture. Approximately 0.5 g were weightedon an analytical balance. 100 mL NMP and 25 mL dibutylamine were added.The mixture was titrated with 0.1 M hydrochloric acid using a solventpH-electrode and a Metrohm titration system.

Determination of the Water Content and the Hydroxyl Groups was performedwith Karl-Fischer method according to DIN 51777 and DIN 53240.

-   Mowiol® 15-97 was a powdered partially hydrolyzed polyvinyl alcohol,    viscosity 15 mPas (4% aqueous solution at 20° C.), degree of    hydrolysis about 81.5 mol %.-   Culminal® MPHC 100 was a methylhydroxypropylcellulose with a    viscosity of 90-125 mPas at 2% in water.-   Pergascript Red I 6B was a dye with CAS no. 50292-95-0.-   Solvesso® 200 ND was an aromatic hydrocarbon fluid, destillation    range from 235-290° C., naphthalene content about 0.9%.-   Poly-L-lysine was used as 50% in water with M_(w)˜2000 Da (20%    α-polylysine and 80% ε-polylysine).-   Polyester-Polyol A was a reaction product of trimethylolpropan (TMP)    and ε-caprolacton, a clear liquid with hydroxy value of 564 mg    KOH/g, acid value below 1 mg KOH/g, mean molecular weight 300 g/mol,    and a viscosity of about 170 mPas (60° C.).

Synthesis of NCO-Functionalized Oligoester (Product A)

A mixture of 57.4 g Polyester-Polyol A, 120 g methylethylketone and128.4 g Isophoronediisocyanate (IPDI) was heated to 100° C. and gentlystirred. The NCO-content was regularly measured to ensure the conversionrate. NCO content before reaction was about 15.86%. NCO content at theend of the reaction was about 8.64%, indicating for a conversion rate ofabout 91%. 247 g of the resulting product A was mixed with 150 g ofSolvesso® 200 ND. The mixture was then heated up to 60° C. in a rotaryevaporator, under 40 mbar pressure, in order to gently evaporate themethylethylketone from the mixture. The resulting Product A in Solvesso200 ND had a solid content of 48.9%, and a NCO content of about 6.66%.

Example 1: Microcapsules with Tetraethylene Pentamine (B1)

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 203.2100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 201.8 100 Product A44.6 100 Pergascript Red I 6B 0.5 100 Feed 2 Tetraethylene 3.2 100pentamine (B1) Water 46.8 100

The microcapsules were prepared by the following operation mode: Preparethe reactor charge by mixing all components together, and slowly add theFeed 1 into the reactor. The dye Pergascript Red I 6B was dissolved inthe Solvesso® 200 ND. Disperse the mixture using a disperser runningwith 6000 rpm for 15 minutes. Equip the reactor with an anchor stirringblade, and slowly add the Feed 2 into the reactor mixture over atime-period of 60 minutes. Afterwards heat-up the reaction mixture to80° C. within 60 minutes, and further stir at 80° C. for additionally120 minutes. Cool down the mix to room temperature.

Example 2 (Comparative): Microcapsules with Isophorone Diisocyanate (C)and Polylysine (B1)

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 185.3100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 199.6 100Isophorone diisocyanate 13.1 100 Pergascript Red I 6B 0.4 100 Feed 2Polylysine (B1) 73.8 50 Water 26.2 100 Feed 3 Sodium hydroxide 4.4 25

The microcapsules were prepared by the following operation mode: Preparethe reactor charge by mixing all components together, and slowly add theFeed 1 into the reactor. Disperse the mixture using a disperser runningwith 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor.Equip the reactor with an anchor stirring blade, and slowly add the Feed2 into the reactor mixture over a time-period of 60 minutes. Afterwardsheat-up the reaction mixture to 80° C. within 60 minutes, and furtherstir at 80° C. for additionally 120 minutes. Cool down the mix to roomtemperature.

Example 3: Microcapsules with Polylysine (B1)

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 210.9100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 211.6 100 Product A25.4 100 Pergascript Red I 6B 0.5 100 Feed 2 Polylysine (B1) 25.2 50Water 24.8 100 Feed 3 Sodium hydroxide 4.4 25

The microcapsules were prepared by the following operation mode: Preparethe reactor charge by mixing all components together, and slowly add theFeed 1 into the reactor. Disperse the mixture using a disperser runningwith 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor.Equip the reactor with an anchor stirring blade, and slowly add the Feed2 into the reactor mixture over a time-period of 60 minutes. Afterwardsheat-up the reaction mixture to 80° C. within 60 minutes, and furtherstir at 80° C. for additionally 120 minutes. Cool down the mix to roomtemperature.

Example 4: Microcapsules with (B1) Polylysine

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 196.2100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 211.6 100 Product A31.9 100 Pergascript Red I 6B 0.5 100 Feed 2 Polylysine (B1) 15.8 50Water 24.8 100 Feed 3 Sodium hydroxide 4.4 25

The microcapsules were prepared by the following operation mode: Preparethe reactor charge by mixing all components together, and slowly add theFeed 1 into the reactor. Disperse the mixture using a disperser runningwith 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor.Equip the reactor with an anchor stirring blade, and slowly add the Feed2 into the reactor mixture over a time-period of 60 minutes. Afterwardsheat-up the reaction mixture to 80° C. within 60 minutes, and furtherstir at 80° C. for additionally 120 minutes. Cool down the mix to roomtemperature.

Example 5: Analytic Results of the Capsule Suspensions

The capsule size was determined by Dynamic Light Scattering.Measurements were performed using a Malvern Particle Sizer 3600E type,and following a standard procedure described in the literature. D(0.5)is the median diameter of the volume of distribution. It is expressed inmicrons, and it indicates that 50% of the sample has a size smaller thanthat value, whereas 50% have a larger size. D(0.1) indicates that 10% ofthe sample has a size smaller than that value, whereas 90% have a largersize. D(0.9) indicates that 90% of the sample has a size smaller thanthat value, whereas 10% have a larger size.

The Total Solid Content (TSC) and the Evaporation Rate (ER) weredetermined as follows: The amount of total solid was determined bydrying a given amount m₀ of the capsule dispersion in the drying oven at105° C. for 2 hours. After drying the new sample weight m₁ wasdetermined and solid content was calculated as follow: SC%=[1−[(m₀−m₁)/m₀]]×100. The evaporation rate was obtained by furtherdrying the same sample at 13° C. for 1 additional hour, giving rise toanew sample weight m₂. The evaporation rate was calculated as follow: ER%=[(m₁−m₂)/m₁]]×100. The results are summarized in the following Table.

SC_(the) ^(a)) SC_(exp) ^(b)) ER^(c)) D (0.1) D (0.5) D (0.9) Example 140.0% 37.0% 10.2%  3.27 μm 5.25 μm 8.58 μm Example 2^(d)) 40.0% 39.6%3.5% 3.10 μm 4.78 μm 7.82 μm Example 3 40.0% 39.5% 2.4% 3.42 μm 5.70 μm9.69 μm Example 4 39.1% 38.6% — 3.25 μm 5.02 μm 7.90 μm ^(a))SC_(the)corresponds to the theoretical solid content ^(b))SC_(exp) correspondsto the solid content experimentally measured ^(c))ER corresponds to theevaporation rate ^(d))comparative

The results demonstrated that the inventive microcapsules had similarparticle size and evaporation rate as microcapsules based on the hardlybiodegradable isocyanate isophorone diisocyanate used in Example 2. Forcomparison, the poly(ester-urethane) containing at least 2 isocyanategroups (component A) of the present invention has several ester bondswhich allow for a good biodegradability of this microcapsule type at asimilar particle size and evaporation rate.

Example 6: Capsule Mechanical Stability

Test method: A thin layer chromatography aluminium sheet coated withsilica gel was cut into a piece of 10 cm*20 cm. The 200 μm casting bladewas placed on the sheet and filled with the capsule dispersion. Thecasting blade then was pulled over the aluminium sheet resulting into adispersion layer with an approximate thickness of 200 μm. Afterwards thesheet was dried at room temperature. The round tip of a magnetic stirbar was used to put mechanical stress on the microcapsule layer withoutdamaging the silica surface.

Samples of the Examples 1 to 4 were tested. No coloration due to theencapsulated Pergascript Red I 6B was observed before the mechanicaltrigger in all the samples. The dye could be released due to themechanical stress and showing a fine line.

The results demonstrated that the inventive microcapsules had similarmechanical stability as microcapsules based on the hardly biodegradableisocyanate isophorone diisocyanate used in Example 2. For comparison,the poly(ester-urethane) containing at least 2 isocyanate groups(component A) of the present invention has several ester bonds whichallow for a good biodegradability of this microcapsule type at a similarmechanical stability.

Example 7: Pesticidal Microcapsules with Tetraethylene Pentamine (B1)

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 203.2100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 201.8 100 Product A44.6 100 Pesticide 0.5 100 Feed 2 Tetraethylene pentamine (B1) 3.2 100Water 46.8 100

The microcapsules are prepared by the operation mode as described inExample 1. Instead of the dye water-insoluble pesticides are used:

Example 7A): pyraclostrobin (water solubility 1.9 mg/I at 20° C.)Example 7B): acetochlor (water solubility 0.2 g/I at 20° C.)Example 7C): fipronil (water solubility 4 mg/I at 20° C.)

The particle size and evaporation rate are determined as in Example 5and the results are similar to those of Example 1 in the Table ofExample 5. The mechanical stability is determined as in Example 6 andthe results are similar to those of Example 1.

Example 8: Pesticidal Microcapsules with Polylysine (B1)

Quantity Concentration [g] [%] Charge Mowiol 15-79 50.0 10 Water 210.9100 Culminal MHPC 100 100.0 5 Feed 1 Solvesso 200 ND 211.6 100 Product A25.4 100 Pesticide 0.5 100 Feed 2 Polylysine (B1) 25.2 50 Water 24.8 100Feed 3 Sodium hydroxide 4.4 25

The microcapsules are prepared by the operation mode as described inExample 3. Instead of the dye water-insoluble pesticides are used:

Example 8A): pyraclostrobin (water solubility 1.9 mg/I at 20° C.)Example 8B): acetochlor (water solubility 0.2 g/I at 20° C.)Example 8C): fipronil (water solubility 4 mg/I at 20° C.).

The particle size and evaporation rate are determined as in Example 5and the results are similar to those of Example 3 in the Table ofExample 5. The mechanical stability is determined as in Example 6 andthe results are similar to those of Example 3.

1. A microcapsule comprising a capsule core and a polymeric shell,wherein the core comprises only hydrophobic components and the shellcomprises in polymerized form: A) at least one poly(ester-urethane)comprising at least 2 isocyanate groups, obtainable by reacting at leastone polyester-polyol comprising at least 2 OH groups with at least onepolyisocyanate comprising at least 2 NCO groups, and; B1) at least onepolymeric polyamine having a weight average molecular weight of at least300 g/mol and comprising at least 3 amino groups reactive towards NCOgroups.
 2. The microcapsule according to claim 1, wherein thepoly(ester-urethane) is a reaction product of the polyester-polyol withthe polyisocyanate which is selected from the group consisting ofhexamethylene diisocyanate, tetramethylene diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, isophoronediisocyanate, 2,4- and2,6-toluylene diisocyanate and isomer mixtures thereof, 2,4′- and4,4′-diphenylmethane diisocyanate and isomer mixtures, biurets,allophanates and/or isocyanurates or mixtures thereof.
 3. Themicrocapsule according to claim 1, wherein the polyester-polyol is apolylactonpolyol which comprises 2 or 3 OH groups.
 4. The microcapsuleaccording to claim 1, wherein the polyester-polyol is a compound of theformulae (2), (5), or mixtures thereof

wherein R^(a) is selected from linear or branched C₁-C₁₀-alkylene groupand C₃-C₂₀-cycloaliphatic radicals having 3 to 10 ring carbon atoms,R^(b) is a linear or branched C₁-C₁₀-alkantriyl group, l, m and n areindependently an integer of 1 to 100, with the proviso that in theformula (2) n+m is an integer of 2 to 100, in the formula (5) n+m+l isan integer of 2 to
 100. 5. The microcapsule according to claim 1,wherein the polyester-polyol has a weight-average molecular weight offrom 200 to 3000 g/mol.
 6. The microcapsule according to claim 1,wherein the shell comprises in polymerized form a component B1) selectedfrom the group consisting of polyaminosaccharides, polyamidoamines,polyesteramines, polyetheramines, polyvinylamines, polyaminoacids andcombinations thereof.
 7. The microcapsule according to claim 1, whereinthe shell comprises in polymerized form a component B1) which comprisesat least one polyamidoamine.
 8. The microcapsule according to claim 7,wherein the at least one polyamidoamine is polylysine and wherein thepolylysine has an average molecular weight from of 300 to 4000 g/mol. 9.The microcapsule according to claim 1, wherein a core-shell ratio (w/w)of the microcapsule is 20:1 to 1:1.
 10. The microcapsule according toclaim 1, wherein a mean particle size of the microcapsule d(0.5) is inthe range from 0.5 μm to 50 μm.
 11. The microcapsule according to claim1, wherein the hydrophobic components comprise a pesticide.
 12. Themicrocapsule according to claim 1, wherein the hydrophobic componentscomprise a pesticide and an oil body selected from the group consistingof vegetable oils, modified vegetable oils, synthetic (tri)glycerides,fatty acid alkyl esters, fatty acid alkyl esters based on C6-C22 fattyacids, mineral oils, hydrocarbons, saturated or unsaturated C6-C30-fattyacids, aromatic compounds, esters of linear C6-C22-fatty acids andmixtures thereof.
 13. A microcapsule dispersion comprising at least onemicrocapsule according to claim
 1. 14. A process for the preparation ofthe microcapsule according to claim 1, wherein the capsule core isobtainable by a) providing a premix (Ib) comprising the hydrophobiccomponent(s) to be encapsulated (Cb), and at least one component (A) asdefined in claim 1, and b) mixing the premix (Ib) provided in step a)with a hydrophilic medium comprising at least one hydrophilic protectivecolloid, at least one component (B1) as defined in claim 1, and reactinga resulting mixture to form microcapsules dispersed in the hydrophilicmedium.
 15. A method of controlling phytopathogenic fungi and/orundesired plant growth and/or undesired insect or mite attack and/or forregulating the growth of plants, wherein the microcapsule according toclaim 1, where the hydrophobic components comprise a pesticide, isallowed to act on the respective pests, their environment or the cropplants to be protected from the respective pest, on the soil and/or onundesired plants and/or on the crop plants and/or on their environment.16. The microcapsule according to claim 9, wherein the core-shell ratio(w/w) of the microcapsule is 10:1 to 2:1.
 17. The microcapsule accordingto claim 16, wherein the core-shell ratio (w/w) of the microcapsule is6:1 to 3:1.
 18. The microcapsule according to claim 10, wherein the meanparticle size of the microcapsule d(0.5) is in the range from 0.7 μm to30 μm.
 19. The microcapsule according to claim 11, wherein thehydrophobic components further comprise an oil body.
 20. The processaccording to claim 14, wherein said providing a premix comprisesproviding the premix further comprising a hydrophobic medium that isliquid at 20° C. and 1023 mbar different from the (Cb).